CN1149230C - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Abstract

A catalyst for olefin polymerization which comprises a novel transition metal compound and has excellent activity in olefin polymerization; and a method of polymerizing an olefin using this catalyst. The catalyst comprises a transition metal compound (A-1) represented by formula (I) or a transition metal compound (A-2) represented by formula (II) and optionally further contains at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminumoxy compounds (B-2), and compounds (B-3) which react with the transition metal compound (A-1) or (A-2) to form an ion pair. In the formula (II), M represents a transition metal in Groups 3 to 11 of the Periodic Table; m is an integer of 1 to 3 in formula (I) and is an integer of 1 to 6 in formula (II); Q represents -N= or -C(R<2>)=; A represents -O-, -S-, -Se-, or -N(R<6>)-; R<1> to R<6> each represents hydrogen, a hydrocarbon group, etc., provided that two or more of R<1> to R<6> may be bonded to each other to form a ring; n is a number equal to the valence of M; and X represents halogeno, a hydrocarbon group, etc.

Description

Olefin polymerization catalyst and olefin polymerization method

field of invention

The present invention relates to olefin polymerization catalysts containing novel transition metal compounds, and to a method for olefin polymerization using the olefin polymerization catalysts.

Background technique

As olefin polymerization catalysts, "Kaminsky catalysts" are well known. The Kaminsky catalyst has a relatively high polymerization activity, and the polymer with a narrow molecular weight distribution can be obtained by using this catalyst. Transition metal compounds known to be useful in Kaminsky catalysts are, for example, bis(cyclopentadienyl)zirconium dichloride (see Japanese Laid-Open Patent No. 19309/1983) and ethylene bis(4,5,6,7 -tetrahydroindenyl)zirconium (see Japanese Laid-Open Patent No. 130314/1986). It is known that the use of different transition metal compounds when polymerizing makes a large difference in the olefin polymerization activity and the properties of the olefin formed. In recent years, it has been proposed to use a transition metal compound having a diimine ligand structure as a new olefin polymerization catalyst (see International Patent Publication No. 9623010).

Furthermore, polyolefins generally have excellent mechanical properties, so they can be used in many fields, for example, in the field of various molded articles. However, various demands have been placed on polyolefins in recent years, and thus polyolefins having different properties are required. In addition, improvement in productivity is also desired.

Under the above circumstances, it is required to develop an olefin polymerization catalyst having excellent olefin polymerization activity and capable of producing polyolefin having excellent properties.

The present invention has been accomplished in consideration of the above-mentioned situation of the prior art. SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst comprising a novel transition metal compound and having excellent olefin polymerization activity. Another object of the present invention is to provide a method for olefin polymerization using the catalyst.

Overview of the invention

A first example of the olefin polymerization catalyst of the present invention includes a transition metal compound (A-1) represented by the following general formula (I):

Wherein, M is the transition metal atom of Group 3 to Group 11 of the periodic table of elements,

m is an integer of 1-3,

Q is a nitrogen atom or a carbon atom with a substituent R ² ,

A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom with a substituent R ⁶ ,

R ¹ -R ⁶ can be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, and phosphorus-containing groups , a silicon-containing group, a germanium-containing group or a tin-containing group, two or more of these groups can be connected to each other to form a ring, when m is 2 or greater, multiple R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ may be the same or different, a group of R ¹ -R ⁶ groups contained in one ligand and a group of R ¹ -R ⁶ groups contained in another ligand may be connected together,

n is a number satisfying the valence of M,

X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue , a silicon-containing group, a germanium-containing group or a tin-containing group, when n is 2 or more, multiple Xs may be the same or different, and multiple Xs may be connected to each other to form a ring.

In the transition metal compound (A-1) represented by the general formula (I), Q is a carbon atom with a substituent ^R , it can be represented by the following general formula (Ia):

Wherein, M, m, A, R ¹ -R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁶ , n and X in the general formula (I).

The transition metal compound (A-1) represented by general formula (Ia) is preferably a compound in which M is selected from transition metal atoms of Groups 8 to 10 of the periodic table. The compound of general formula (Ia) preferably wherein A is a nitrogen atom with a substituent ^R and ^R is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group. In addition, compounds of formula (Ia) wherein A is an oxygen atom are also preferred. In addition, compounds of formula (Ia) wherein A is a sulfur atom are also preferred. Compounds of formula (Ia) in which A is a selenium atom are also preferred.

In the transition metal compound represented by general formula (Ia), R ³ and R ⁴ are connected together to form an aromatic ring compound, which can be represented by the following formula (Ib):

Wherein, M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n and X are the same as M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n in general formula (I) and X have the same meaning.

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁶ in the general formula (I),

R ¹ , R ² and R ⁵ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ can be the same or different, and a group of R ¹ , R ² , R ⁵ -R ¹⁰ contained in one ligand can be the same as that contained in another ligand A group of R ¹ , R ² , R ⁵ -R ¹⁰ are connected.

The transition metal compound (A-1) represented by general formula (Ib) is preferably a compound of general formula (Ib) in which M is selected from transition metal atoms of Groups 8 to 10 of the periodic table. The compound of general formula (Ib) preferably wherein A is a nitrogen atom with a substituent ^R and ^R is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group. In addition, compounds of formula (Ib) wherein A is an oxygen atom are also preferred. In addition, compounds of formula (Ib) wherein A is a sulfur atom are also preferred. Compounds of formula (Ib) in which A is a selenium atom are also preferred.

In the transition metal compound (A-1) represented by the general formula (I), Q is a nitrogen atom and R ³ and R ⁴ The compound that is connected together to form an aromatic ring can be represented by the following formula (Ic):

Wherein, M, m, A, R ¹ , R ⁵ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ⁵ , R ⁶ , n and X in general formula (I) .

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁶ in the general formula (I),

R ¹ and R ⁵ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be the same or different, a group of R ¹ , R ⁵ -R ¹⁰ included in one ligand may be combined with a group of R ¹ , R ⁵ - included in another ligand ^R10 is connected.

The transition metal compound (A-1) represented by general formula (Ic) is preferably a compound of formula (Ic) in which M is selected from transition metal atoms of Groups 3-5 and Groups 8-10 of the Periodic Table of Elements. Preferred compounds of general formula (Ic) are also those in which A is a nitrogen atom with a substituent R ⁶ . In addition, compounds of formula (Ic) wherein A is an oxygen atom are also preferred. In addition, compounds of formula (Ic) wherein A is a sulfur atom are also preferred. Compounds of formula (Ic) in which A is a selenium atom are also preferred.

Another example of the olefin polymerization catalyst of the present invention includes a transition metal compound (A-2) represented by the following general formula (II):

Wherein, M is the transition metal atom of Group 3 to Group 11 of the periodic table of elements,

m is an integer of 1-6,

Q is a nitrogen atom or a carbon atom with a substituent R ² ,

A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom with a substituent R ⁶ ,

R ¹ -R ⁴ and R ⁶ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, Phosphorous groups, silicon-containing groups, germanium-containing groups or tin-containing groups, two or more of these groups can be connected to each other to form a ring, when m is 2 or greater, multiple R ¹ , R ² , R ³ , R ⁴ or R ⁶ can be the same or different, a set of R ¹ -R ⁴ and R ⁶ groups contained in one ligand and a set of R ¹ -R ⁴ contained in another ligand and the ^R6 group can be linked,

n is a number satisfying the valence of M,

X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue , a silicon-containing group, a germanium-containing group or a tin-containing group, when n is 2 or more, multiple Xs may be the same or different, and multiple Xs may be connected to each other to form a ring.

In the transition metal compound (A-2) represented by the general formula (II), Q is a carbon atom with a substituent ^R , it can be represented by the following general formula (II-a):

Wherein, M, m, A, R ¹ -R ⁴ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁴ , R ⁶ , n and X in general formula (II) .

The transition metal compound (A-2) represented by general formula (II-a) is preferably a compound of formula (II-a) in which M is a transition metal atom selected from titanium, zirconium or hafnium. The preferred general formula (II-a) compound also has wherein A is a nitrogen atom with a substituent R ⁶ and R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, A boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. In addition, the compound of formula (II-a) wherein A is an oxygen atom is also preferred. In addition, the compound of formula (II-a) wherein A is a sulfur atom is also preferred. Compounds of formula (II-a) wherein A is a selenium atom are also preferred.

In the transition metal compound (A-2) represented by general formula (II-a), R ³ and R ⁴ are connected together to form an aromatic ring compound, which can be represented by the following formula (II-b):

Among them, M, m, A, R ¹ , R ² , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ² , R ⁶ , n and X in the general formula (II) .

When m is 1, A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent ^R6 , and when m is 2 or more, multiple A can be the same or different, and they are respectively an oxygen atom, a sulfur atom, a selenium atom atom or a nitrogen atom with a substituent ^R6 , and at least one A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent ^R6 .

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴ and R ⁶ in the general formula (II),

R ¹ , R ² and R ⁶ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be the same or different, and a group of R ¹ , R ² , R 6 -R 10 included in one ligand may be the same as a group of R ⁶ -R ¹⁰ included in another ligand R ¹ , R ² , and R ⁶ -R ¹⁰ are connected.

The transition metal compound (A-2) represented by general formula (II-b) is preferably a compound of formula (II-b) in which M is a transition metal atom selected from titanium, zirconium or hafnium. The preferred general formula (II-b) compound also has wherein A is a nitrogen atom with a substituent R ⁶ and R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, A boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. In addition, compounds of formula (II-b) wherein A is an oxygen atom are also preferred. In addition, the compound of formula (II-b) wherein A is a sulfur atom is also preferred. Compounds of formula (II-b) in which A is a selenium atom are also preferred.

In the transition metal compound (A-2) represented by the general formula (II), Q is a nitrogen atom and R ³ and R ⁴ are connected together to form an aromatic ring compound can be represented by the following formula (II-c):

Wherein, M, m, A, R ¹ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ⁶ , n and X in the general formula (II).

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴ and R ⁶ in the general formula (II),

R ¹ and R ⁶ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ can be the same or different, a group of R ¹ , R 6 -R ¹⁰ contained in one ligand can be the same as a group of R ¹ , ^{R 6 -R 10} contained in another ligand connect.

The transition metal compound (A-2) represented by general formula (II-c) is preferably M selected from the formula (II-c) compound of the transition metal atoms of Group 3-5 and Group 8-10 of the Periodic Table of Elements . Also preferred are compounds of general formula (II-c) wherein A is a nitrogen atom with a substituent R ⁶ . In addition, compounds of formula (II-c) wherein A is an oxygen atom are also preferred. In addition, compounds of formula (II-c) wherein A is a sulfur atom are also preferred. Compounds of formula (II-c) wherein A is a selenium atom are also preferred.

In addition to the transition metal compound (A-1) or (A-2), the olefin polymerization catalyst of the present invention also includes at least one compound (B) selected from:

(B-1) an organometallic compound,

(B-2) an organoaluminum oxy compound, or

(B-3) A compound that reacts with the transition metal compound (A-1) or (A-2) to form an ion pair.

The olefin polymerization catalyst of the present invention contains a support (C) in addition to the transition metal compound (A-1) or (A-2) and the compound (B).

Brief description of the drawings

Figure 1 and Figure 2 are schematic diagrams of the preparation method of the olefin polymerization catalyst of the present invention, respectively.

Best Mode for Carrying Out the Invention

A first example of the olefin polymerization catalyst of the present invention includes a transition metal compound (A-1) represented by the following general formula (I):

In the general formula (I), dotted lines (---) in N---M and A---M indicate that a dative bond is formed or not formed, but at least one of them is preferably a dative bond.

The coordinate bond can be confirmed by NMR, TR, X-ray crystal structure analysis and the like.

In the general formula (I), M is a transition metal atom from Group 3 (including lanthanide) to Group 11 of the periodic table of elements, and examples of these metal atoms include scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, Niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel and palladium. Among them, preferred are metal atoms of Groups 3 to 5 and Groups 8 to 10, such as scandium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel and palladium. Most preferred are metal atoms of Groups 4, 5 and 8-10, such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel and palladium. Preferred are metal atoms of Groups 8-10, such as iron, cobalt, rhodium, nickel and palladium.

m is an integer of 1-3, preferably an integer of 1-2.

Q is a nitrogen atom (-N=) or a carbon atom having a substituent R ² (-C(R ² )=),

A is an oxygen atom (-O-), a sulfur atom (-S-), a selenium atom (-Se-) or a nitrogen atom (-N(R ⁶ )-) having a substituent R ⁶ ,

R ¹ -R ⁶ can be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, and phosphorus-containing groups , silicon-containing groups, germanium-containing groups or tin-containing groups, two or more of these groups can be linked together to form a ring.

R ¹ - ^{R 6} are preferably hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, hydrocarbon-substituted silyl groups, hydrocarbon-substituted silyloxy groups, alkoxy groups, alkylthio groups, aryloxy groups, Arylthio, acyl, ester, thioester, amido, imido, amino, imino, sulfonyl ester, sulfonylamino, cyano, nitro, carboxyl, sulfo, mercapto or hydroxy.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of hydrocarbon groups include straight or branched chain alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; straight-chain or branched alkenyl groups having 2-30 carbon atoms, preferably 2-20 carbon atoms, such as vinyl, alkenyl Propyl and isopropenyl; having 2-30 carbon atoms, preferably straight-chain or branched alkynyl having 2-20 carbon atoms, such as ethynyl and propynyl; having 3-30 carbon atoms, relatively Saturated cyclic hydrocarbon groups preferably having 3-20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; unsaturated cyclic hydrocarbon groups having 5-30 carbon atoms, such as cyclopentadiene Alkenyl, indenyl and fluorenyl; aryl having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthrenyl and anthracenyl; and alkyl-substituted aryl groups such as tolyl, cumyl, tert-butylphenyl, dimethylphenyl and di-tert-butylphenyl.

In the above hydrocarbon groups, hydrogen atoms may be replaced by halogen atoms. Examples of such halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms include trifluoromethyl, pentafluorophenyl and Chlorophenyl.

In the above-mentioned hydrocarbon groups, a hydrogen atom may be substituted by another hydrocarbon group, and examples of such aryl-substituted alkyl groups include benzyl and cumyl.

In addition, the above-mentioned hydrocarbon group may be a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group (carbonato), a hydroxyl group, a peroxy group, and a carboxyl group Acid anhydride groups; nitrogen-containing groups, such as amino, imino, amido, imido, hydrazino, hydrazino, nitro, nitroso, cyano, isocyano, cyano, amidino, heavy Nitrogen groups and ammonium salts derived from amino groups; boron-containing groups such as boronyl, methylene and diboryl groups; sulfur-containing groups such as mercapto, thioester, dithioester, alkylthio arylthio, sulfonyl, thioether, thiocyanate, isocyanthiocyanate, sulfonate, sulfonylamino, thiocarboxy, dithiocarboxy, sulfo, sulfonyl, sulfinyl and sulfur groups; phosphorus-containing groups such as phosphido, phosphoryl, thiophosphoryl and phosphato; silicon-containing groups; germanium-containing groups or tin-containing groups.

Among the above groups, it is preferred to have 1-30 carbon atoms, preferably straight-chain or branched-chain alkyl groups with 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; aryl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as phenyl, naphthalene Base, biphenyl, terphenyl, phenanthrenyl and anthracenyl; substituted aryl, such as the above-mentioned aryl having 1-5 substituents, such as halogen atoms, 1-30 carbon atoms , preferably an alkyl or alkoxy group having 1-20 carbon atoms, an aryl or aryloxy group having 6-30 carbon atoms, preferably an aryl group or aryloxy group having 6-20 carbon atoms.

Examples of heterocyclic compound residues include residues of nitrogen-containing compounds (such as pyrrole, pyridine, pyrimidine, quinoline, and triazine), oxygen-containing compounds (such as furan and pyran), and sulfur-containing compounds (such as thiophene) as well as residues with Substituents (such as alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms) of these heterocyclic compound residues.

Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group and phosphorus-containing group represented by R ¹ to R ¹⁶ include the groups described above as substituents and which may be contained in the hydrocarbon group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Examples of hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diethylsilyl, A phenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-tert-butylsilyl group and a dimethyl(pentafluorophenyl)silyl group. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylsilyl, and dimethylsilyl are preferred. ylsilyl and triphenylsilyl. Most preferred are trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy group.

Examples of the germanium-containing group or the tin-containing group include groups in which silicon is replaced by germanium or tin in the above-mentioned silicon-containing group.

The above-mentioned examples of the groups represented by R ¹ -R ⁶ are described in more detail below.

For oxygen-containing groups, preferred examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy; aryloxy Preferred examples of acyl groups include phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy; preferred examples of acyl groups include formyl, acetyl, benzyl, acyl, p-chlorobenzoyl and p-methoxybenzoyl; preferred examples of ester groups include acetoxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl .

For nitrogen-containing groups, preferred examples of amido groups include acetamido, N-methylacetamido and N-methylbenzamido; examples of preferred amino groups include dimethylamino, ethylmethylamino and Diphenylamino; preferred examples of imino groups include acetimino and benzimino; preferred examples of imino include methylimino, ethylimino, propylimino, butylimino and phenylimino.

For sulfur-containing groups, preferred examples of alkylthio include methylthio and ethylthio; preferred examples of arylthio include phenylthio, methylphenylthio and naphthylthio; preferred thioester groups Examples include acetylthio, benzoylthio, methylthiocarbonyl and phenylthiocarbonyl; preferred examples of sulfonate groups include methylsulfonate, ethylsulfonate and phenylsulfonic acid Ester group; Desirable examples of sulfonylamino group include phenylsulfonylamino, N-methylsulfonylamino and N-methyl-p-toluenesulfonylamino.

Two or more of the R ¹ -R ⁶ groups, preferably adjacent groups, can be connected to each other to form an alicyclic ring, aromatic ring or hydrocarbon ring containing heteroatoms (such as nitrogen atoms). These rings may also have a substituent.

In the general formula (I), when m is 2 or more, a plurality of R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ may be the same or different.

When m is 2 or more, a group of R ¹ -R ⁶ groups contained in one ligand and a group of R ¹ -R ⁶ groups contained in another ligand may be linked together. In such cases, the backbone of the linking group formed linking such R ¹ -R ⁶ groups together preferably contains 3 or more atoms.

X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue , silicon-containing groups, germanium-containing groups or tin-containing groups.

n is a number satisfying the valence of M, preferably an integer of 0-5, preferably an integer of 1-4, most preferably an integer of 1-3.

When n is 2 or more, a plurality of X groups may be the same or different, and a plurality of X groups may be connected to each other to form a ring.

Halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include the same groups as described above for R ¹ -R ⁶ . Specifically, it may be an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkane having 3 to 30 carbon atoms groups such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; aryl such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthrenyl, but not limited to these groups. The hydrocarbyl group may also include a halogenated hydrocarbyl group, especially a group having 1 to 30 carbon atoms and having at least one hydrogen atom replaced with a halogen atom. Among them, hydrocarbon groups having 1 to 20 carbon atoms are preferred.

Examples of the heterocyclic compound residue include the same groups as described above for R ¹ -R ⁶ .

Examples of the oxygen-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, mention may be made of hydroxyl; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy; arylalkoxy, such as phenylmethoxy and phenylethoxy; acetoxy; and carbonyl, but are not limited to these groups.

Examples of the sulfur-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, there may be mentioned sulfonate groups such as methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trifluoromethanesulfonate, Tosylate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; sulfinate groups such as methylsulfinate, benzene sulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio; and arylthio , but not limited to these groups.

Examples of the nitrogen-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, there can be mentioned amino; alkylamino such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; and arylamino or alkyl Arylamino groups such as, but not limited to, phenylamino, diphenylamino, xylylamino, dinaphthylamino and methylphenylamino groups.

Examples of the boron-containing group include BR ₄ (R is hydrogen, an alkyl group, an aryl group (may have a substituent), a halogen atom, etc.).

Examples of phosphorus-containing groups include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tricresylphosphine; phosphites groups such as methyl phosphite group, ethyl phosphite group and phenyl phosphite group; phosphonic acid group and phosphinic acid group, but not limited to these groups.

Examples of the silicon-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tripropylsilyl, Cyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, trimethylphenylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylmethylsilyl silyl ether groups; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

Examples of the germanium-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, there may be mentioned groups in which silicon is replaced by germanium in the above-mentioned silicon-containing groups.

Examples of the tin-containing group include the same groups as described above for R ¹ -R ⁶ . Specifically, there may be mentioned groups in which silicon is substituted by tin in the above-mentioned silicon-containing groups.

Examples of halogen-containing groups include fluorine-containing groups such as PF ₆ and BR ₄ ; chlorine-containing groups such as ClO ₄ and SbCl ₆ ; and iodine-containing groups such as IO ₄ , but are not limited to these groups.

Examples of the aluminum-containing group include AlR ₄ (R is hydrogen, an alkyl group, an aryl group (may have a substituent), a halogen atom, etc.), but are not limited to these groups.

In the transition metal compound (A-1) represented by the general formula (I), Q is a carbon atom with a substituent ^R , it can be represented by the following general formula (Ia):

Wherein, M, m, A, R ¹ -R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁶ , n and X in the general formula (I).

In the transition metal compound (A-1) represented by the general formula (Ia), two or more of the R ¹ -R ⁶ groups may be linked together to form a ring. A compound in which two or more of R ¹ -R ⁶ groups, such as R ³ and R ⁴ together form an aromatic ring is, for example, a compound represented by the following general formula (Ib):

In the above general formula, M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n and X are the same as M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n and X have the same meanings.

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁶ in the general formula (I),

R ¹ , R ² and R ⁵ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ can be the same or different, and a group of R ¹ , R ² , R ⁵ -R ¹⁰ contained in one ligand can be the same as that contained in another ligand A group of R ¹ , R ² , R ⁵ -R ¹⁰ are connected.

Represented by formula (Ia) and m is 2, one set of R ¹ -R ⁶ groups contained in one ligand and another set of R ¹ -R ⁶ groups contained in the other ligand The linked transition metal compound (A-1) is, for example, a compound represented by the following general formula (I-a').

In the above general formula, M, A, R ¹ -R ⁶ , n and X have the same meanings as M, A, R ¹ -R ⁶ , n and X in formula (I).

A' is the same as or different from A, and is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^6' .

R ^1' -R ^6' may be the same as or different from R ¹ -R ⁶ and have the same meaning.

Two or more groups in the R ^1' -R ^6' group, preferably adjacent groups, can be connected to each other to form an alicyclic ring, an aromatic ring and a hydrocarbon ring containing heteroatoms (such as nitrogen atoms) .

Y is a linking group or a single bond for connecting at least one group among R ¹ -R ⁶ with at least one group among R ^1' -R ^6' . Although the linking group is not particularly limited, its structure preferably has a main chain consisting of 3 or more atoms, preferably 4-20 atoms, most preferably 4-10 atoms. The linking group may have a substituent.

The linking group Y is a group containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and the like. Examples of such groups include groups containing chalcogen atoms, such as -O-, -S-, and -Se-; nitrogen-containing groups or phosphorus-containing groups, such as -NH-, -N(CH ₃ ) ₂ , -PH- and -P(CH ₃ ) ₂ -; hydrocarbon groups with 1-20 carbon atoms, such as -CH ₂ -, -CH ₂ -CH ₂ - and -C(CH ₃ ) ₂ -; with 6- Unsaturated rings of 20 carbon atoms, such as residues of benzene, naphthalene, and anthracene; heterocyclic compounds with 3-20 carbon atoms and heteroatoms, such as residues of pyridine, quinoline, thiophene, and furan; silicon-containing groups Groups, such as -SiH ₂ - and -Si(CH ₃ ) ₂ -; tin-containing groups, such as -SnH ₂ - and -Sn(CH ₃ ) ₂ -; and boron-containing groups, such as -BH-, -B ( _CH3 )- and -BF-. Y can also be a single bond.

An example of a compound usable as an olefin polymerization catalyst in the present invention is a compound represented by the following formula (L) and MXk (where M and X have the same meanings as M and X described in formula (I), k It is the compound obtained by reacting the compound represented by the number satisfying the M valence.

Wherein, A and R ¹ -R ⁶ have the same meanings as A and R ¹ -R ⁶ in formula (I).

Desirable examples of compounds represented by MXk include TiCl ₃ , TiCL ₄ , TiBr ₃ , TiBr ₄ , Ti(benzyl) ₄ , Ti(NiMe ₂ ) ₄ , ZrCl ₄ , Zr(NiMe ₂ ) ₄ , Zr(benzyl base) ₄ , ZrBr ₄ , HfCl ₄ , HfBr ₄ , VCL ₄ , VCl ₅ , VBr ₄ , VBr ₅ , Ti(acac) ₃ , complexes of these compounds with THF (tetrahydrofuran), acetonitrile or diethyl ether, but not limited to these compounds.

Examples of the transition metal compound represented by formula (I-a) are listed below, but are not limited to these compounds.

In the following examples, M has the same meaning as M in formula (I-a).

X has the same meaning as X in formula (I-a), which is, for example, halogen such as Cl or Br, or alkyl such as methyl, but is not limited to these groups. When there are a plurality of Xs, they may be the same or different.

n has the same meaning as n in the formula (I-a), which is determined by the valence of the metal M. For example, when two monovalent anions are attached to the metal, n=0 in the case of divalent metals, n=1 in the case of trivalent metals, n=2 in the case of tetravalent metals, n=2 in the case of pentavalent metals In the case of n=3. More specifically, n=2 in the case of Ti(IV), n=2 in the case of Zr(IV), and n=2 in the case of Hf(IV).

In the following examples, Me means methyl, Et means ethyl, iPr means isopropyl, tBu means t-butyl and Ph means phenyl.

Examples of transition metal compounds represented by formula (Ia) wherein two or more of the R ¹ -R ⁶ groups are connected to form a ring are those in which R ^and R ⁴ are connected to form a ring (i.e., the formula ( Compounds represented by Ib), specific examples thereof will first be described.

Examples of the compound represented by the formula (I-b) wherein A is an oxygen atom include the following compounds.

In the above examples, M and n have the same meanings as M and n in formula (I-b). Specific compounds can be obtained by appropriate choice of M and n.

For example, consider a compound of the following general formula.

When X in the above general formula is chlorine, depending on the selection of M, the following compounds can be obtained.

When X in the above general formula is bromine, depending on the choice of M, the following compounds can be obtained.

Thus, from the general formula described above and the general formula described below, specific compounds can be obtained by selecting M and n.

Examples of the compound represented by the formula (I-b) in which A is a sulfur atom include the following compounds.

Examples of the compound represented by the formula (Ib) in which A is a nitrogen atom having a substituent R ⁶ include the following compounds.

Examples of the compound represented by formula (Ib) in which R ¹ and R ² are linked together to form an aromatic ring include the following compounds.

Examples of other compounds represented by formula (I-b) are as follows.

Examples of the compound represented by the formula (I-a) in which m is 2 or more include the following compounds.

Represented by formula (Ia), m is 2 or more and a group of R ¹ -R ⁶ contained in one ligand is linked together with a group of R ¹ -R ⁶ contained in another ligand Examples of the transition metal compound include the following compounds.

In the present invention, the compound represented by the formula (I-a) may be a compound having a group corresponding to the ligand, and the group is connected by an ionic bond or a covalent bond, for example, the following formula (I-a" ) represents the compound:

Among them, M, A, R ¹ -R ⁶ and X have the same meanings as M, A, R ¹ -R ⁶ and X in formula (I), and A' can be the same or different from A, and is an oxygen atom, sulfur Atom, selenium atom or nitrogen atom with substituent R ^6' .

Examples of the compound represented by formula (I-a") include the following compounds.

The transition metal compound represented by formula (I-a) is not subject to any restrictions in preparation, for example, it can be prepared by the following method:

Make the compound represented by formula (L):

Wherein A and R ¹ -R ⁶ have the same meaning as A and R ¹ -R ⁶ in the formula (I), and react with the compound represented by the formula MXk (M and X have M and X in the formula (I) same meaning, k is the number that satisfies the valence of M).

Desirable examples of compounds represented by MXk include TiCl ₃ , TiCL ₄ , TiBr ₃ , TiBr ₄ , Ti(benzyl) ₄ , Ti(NiMe ₂ ) ₄ , ZrCl ₄ , Zr(NiMe ₂ ) ₄ , Zr(benzyl base) ₄ , ZrBr ₄ , HfCl ₄ , HfBr ₄ , VCL ₄ , VCl ₅ , VBr ₄ , VBr ₅ , Ti(acac) ₃ , complexes of these compounds with THF (tetrahydrofuran), acetonitrile or diethyl ether, but not limited to these compounds.

The production method of the transition metal compound represented by the formula (I-a) will be described in more detail below.

First, make the acyl acetonide or thioacyl acetonide react with the primary amine compound of the formula R ¹ -NH ₂ (R ¹ has the same meaning as R ¹ in the formula (Ia), such as an aniline compound or an alkylamine compound), A compound (ligand precursor) for constituting a ligand of a transition metal compound is obtained. More specifically, both starting compounds are dissolved in a solvent. As the solvent, any solvent generally used for this reaction can be used. In particular, alcohol solvents such as methanol or ethanol, or hydrocarbon solvents such as toluene are preferred.

Next, the resulting solution is stirred at room temperature to reflux for about 1-48 hours to introduce substituents on part A, thereby obtaining the corresponding ligand precursor in high yield.

It is also possible to make o-acylphenol, o-acylthiophenol or o-anilide (wherein the substituent has been introduced into part A of formula (Ia)) with formula R ¹ -NH ₂ (R ¹ and ^R in formula (Ia) have The same meaning, such as aniline compound or alkylamine compound) reacts with primary amine compound to prepare ligand precursor compound.

In the synthesis of ligand precursors, acid catalysts such as formic acid, acetic acid or toluenesulfonic acid can be used as catalysts. The use of dehydrating agents (such as molecular sieves, magnesium sulfate and sodium sulfate) or the use of Dean and Stark method for dehydration will facilitate the reaction.

Subsequently, the ligand precursor thus obtained is reacted with a transition metal M-containing compound to synthesize a corresponding transition metal compound. More specifically, the synthesized ligand is dissolved in a solvent, which is subsequently mixed with a metal compound such as a metal halide or metal alkyl, at temperatures ranging from -78°C to room temperature, preferably under reflux It was stirred for 1-48 hours. As the solvent, any solvent generally used for this reaction can be used. In particular, polar solvents such as diethyl ether or THF or hydrocarbon solvents such as toluene are preferred.

The metal M in the synthesized transition metal compound can also be exchanged with another transition metal by conventional methods. For example, when any of ^R1 - ^R6 is hydrogen, non-hydrogen substituents may be introduced at any stage of the synthetic procedure.

In the transition metal compound (A-1) represented by the general formula (Ia), Q is a nitrogen atom and R ³ and R ⁴ The compound that is connected together to form an aromatic ring can be represented by the following formula (Ic):

In the above general formula, M, m, A, R ¹ , R ⁵ , R ⁶ , n and X and M, m, A, R ¹ , R ⁵ , R ⁶ , n and X in the general formula (I) have the same meaning. Each of N---M and A---M represents a dative bond.

R ⁷ -R ¹⁰ have the same meanings as R ¹ -R ⁶ in the general formula (I).

R ¹ and R ⁵ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring.

When m is 2 or more, a plurality of R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be the same or different, and a group of R ¹ , R in one ligand ⁵ -R ¹⁰ may be linked to a set of R ¹ , R ⁵ -R ¹⁰ contained in another ligand.

Represented by formula (Ic), m is 2, and a set of R ¹ , R ⁵ -R ¹⁰ contained in one ligand can be combined with a set of R ¹ , R ⁵ -R contained in another ligand ^{The 10-} linked transition metal compound is, for example, a compound represented by the following formula (I-c').

In the above general formula, M, A, R ¹ , R ⁵ -R ¹⁰ and X have the same meanings as M, A, R ¹ , R ⁵ -R ¹⁰ and X in the general formula (I). R ^1' , R ^5' -R ^10' have the same meanings as R ¹ , R ⁵ -R ¹⁰ .

A' may be the same as or different from A, and is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^6' .

Y is a linking group or a single bond for linking at least one of R ¹ and R ⁵ -R ¹⁰ with at least one of R ^1' and R ^5' -R ^10' together. It has the same meaning as Y in formula (I-a').

Examples of transition metal compounds represented by the general formula (I-c) are described below, but are not limited to these compounds.

In the following examples, M has the same meaning as M in formula (I-c).

X has the same meaning as X in formula (I-c), for example, halogen such as Cl or Br, or alkyl such as methyl, but not limited to these groups. When there are a plurality of Xs, they may be the same or different.

n has the same meaning as n in the formula (I-c), which is determined by the valence of the metal M. For example, when a ligand is coordinated to a metal, n=2 in the case of divalent metals, n=3 in the case of trivalent metals, n=4 in the case of tetravalent metals, and n=4 in the case of pentavalent metals In the case of n=5. More specifically, n=4 in the case of Ti(IV), n=4 in the case of Zr(IV), n=4 in the case of Hf(IV), n=4 in the case of Co(II) = 2, n=2 in the case of Fe(II), n=2 in the case of Rh(II), n=2 in the case of Ni(II), n=2 in the case of Pd(II) .

The production of the transition metal compound represented by formula (I-c) is not limited in any way, for example, the following method can be used.

The transition metal compound represented by the formula (I-c) is prepared by reacting a compound (ligand precursor) serving as a ligand for constituting the transition metal compound with a transition metal M-containing compound.

For example, the ligand precursor can be obtained by phenol or phenol derivatives (when A is an oxygen atom in formula (Ic), thiophenol or a thiophenol derivative (when A is a sulfur atom in formula (Ic)) or aniline or aniline derivatives (when A is a nitrogen atom with R ⁶ ) reacted with a diazo compound, the diazo compound can be prepared by the formula R ¹ -NH ₂ (R ¹ has the same R ¹ in the formula (Ic) The meaning of) primary amine compounds, such as aniline compounds or alkylamine compounds are synthesized. More specifically, both starting compounds are dissolved in a solvent. As the solvent, any solvent generally used for this reaction can be used. In particular, an aqueous solvent is preferred. Subsequently, the formed solution is stirred at a temperature ranging from 0° C. to reflux for about 1-48 hours, thereby obtaining the corresponding ligand in high yield.

Diazo compounds can be prepared by reacting primary amine compounds with sodium nitrite, alkyl nitrite, etc., and strong acids such as hydrochloric acid, but the synthesis method is not limited to this method.

Subsequently, the ligand thus obtained is reacted with a transition metal M-containing compound to synthesize the corresponding transition metal compound. More specifically, the synthesized ligands are dissolved in a solvent. If necessary, the resulting solution can be contacted with a base to form a phenoxide. Next, the solution or phenoxide is mixed with a metal compound (such as a metal halide or metal alkyl) at low temperature, and stirred or refluxed at a temperature ranging from -78°C to room temperature for about 1-48 hours. As the solvent, any solvent generally used for this reaction can be used. In particular, it is preferable to use a polar solvent such as diethyl ether or THF or a hydrocarbon solvent such as toluene. Desirable examples of bases for the preparation of phenoxides include metal salts such as lithium salts (such as n-butyllithium) and sodium salts (such as sodium hydride) and organic bases such as triethylamine and pyridine, but are not limited to these compounds . By varying the feed ratio between the transition metal M-containing compound and the ligand, the number of ligands to be reacted can be adjusted.

According to the nature of the compound, the ligand can be directly reacted with the metal compound without making phenoxide, so that the corresponding transition metal compound can be synthesized. For example, the following compounds can be prepared by directly reacting the ligand with a transition metal halide.

The metal M in the prepared transition metal compound can also be exchanged with another transition metal by any conventional method. When any one of R ¹ and R ⁵ -R ¹⁰ is hydrogen, non-hydrogen substituents may be introduced at any stage of the synthetic steps.

Other examples of the olefin polymerization catalyst of the present invention will be described below.

Other examples of the olefin polymerization catalyst of the present invention include transition metal compounds (A-2) represented by formula (II).

In the above general formula, N---M usually represents a coordinate bond, but the present invention also includes compounds without such a coordinate bond.

In the above general formula, M is a transition metal atom of Group 3 (including lanthanide elements) to Group 11 of the periodic table of elements. Examples of such metal atoms include scandium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, nails, nickel and palladium. Among them, preferred are metal atoms of Group 3 (including lanthanide) to Group 9, such as scandium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt and rhodium. More preferred are Group 3 - Group 5 and Group 9 metal atoms such as titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium and tantalum. Most preferred are metal atoms of Group 4-5, such as titanium, zirconium, hafnium and vanadium, and preferred are metal atoms of Group 4, such as titanium, zirconium and hafnium.

m is an integer of 1-6, preferably an integer of 1-4, most preferably an integer of 1-2.

Q is a nitrogen atom (-N=) or a carbon atom having a substituent R ² (-C(R ² )=),

A is an oxygen atom (-O-), a sulfur atom (-S-), a selenium atom (-Se-) or a nitrogen atom with a substituent R ⁶ ,

R ¹ -R ⁴ and R ⁶ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, Phosphorous groups, silicon-containing groups, germanium-containing groups or tin-containing groups, two or more of these groups can be connected to each other to form a ring, when m is 2 or greater, multiple R ¹ , R ² , R ³ , R ⁴ or R ⁶ can be the same or different, a set of R ¹ -R ⁴ and R ⁶ groups contained in one ligand and a set of R ¹ -R ⁴ contained in another ligand and the ^R6 group can be linked.

Examples of the atoms and groups represented by R ¹ -R ⁴ and R ⁶ are the same as those of R ¹ -R ⁶ in formula (I) above.

When A is a nitrogen atom with a substituent ^R6 , ^R6 is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a Phosphorous groups, silicon-containing groups, germanium-containing groups or tin-containing groups.

When A is an oxygen atom, a sulfur atom or a selenium atom, R ⁴ is preferably a non-hydrogen substituent or a halogen. That is, R ⁴ is preferably a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. ^R4 is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted silyloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, thioester group, amido group, amino group, imido group, imino group, sulfonate group, sulfonylamino group, cyano group, nitro group or hydroxyl group.

When A is an oxygen atom, a sulfur atom or a selenium atom, ^preferred examples of the hydrocarbon group R include 1-30 carbon atoms, preferably straight-chain or branched-chain alkyl groups with 1-20 carbon atoms, such as methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; having 3-30 carbon atoms, preferably 3-20 A saturated cyclic hydrocarbon group of carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; an aryl group having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as benzene Base, benzyl, naphthyl, biphenyl, terphenyl; and alkyl or alkoxy having 1-30 carbon atoms, preferably 1-20 carbon atoms, having 1-30 carbon atoms, Preferably haloalkyl having 1 to 20 carbon atoms, aryl or aryloxy having 6 to 30 carbon atoms, preferably aryl or aryloxy, halogen, cyano, nitro or hydroxyl substituted group.

When A is an oxygen atom, a sulfur atom or a selenium atom, preferred examples of the hydrocarbon-substituted silyl group ^R include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl tert-butylsilyl group and two Methyl(pentafluorophenyl)silyl. Among them, trimethylsilyl, triethylsilyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl tert-butyl methyl Silyl and dimethyl(pentafluorophenyl)silyl.

When A is an oxygen atom, a sulfur atom or a selenium atom, ^R is preferably selected from branched chain alkyl groups with 3-30 carbon atoms, preferably selected from branched chain alkyl groups with 3-20 carbon atoms, such as isopropyl, isopropyl Butyl, sec-butyl, tert-butyl and neopentyl; the above-mentioned groups in which the hydrogen atom is replaced by an aryl group having 6-30 carbon atoms, preferably 6-20 carbon atoms (such as cumyl group) and a saturated cyclic hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Also preferred are aryl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as phenyl, naphthyl, fluorenyl, anthracenyl or phenanthrenyl, or hydrocarbon-substituted silyl groups.

n is a number satisfying the valence of M, preferably an integer of 0-5, preferably an integer of 1-4, most preferably an integer of 1-3.

When n is 2 or more, a plurality of Xs may be the same or different, and may be connected to each other to form a ring.

X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue , silicon-containing groups, germanium-containing groups or tin-containing groups.

Examples of the atom or group represented by X include the same atoms and groups as described above when describing X of the formula (I).

In the transition metal compound (A-2) represented by the general formula (II), Q is a carbon atom with a substituent ^R , it can be represented by the following general formula (II-a):

Wherein, M, m, A, R ¹ -R ⁴ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁴ , R ⁶ , n and X in general formula (II) .

The transition metal compound (A-2) represented by the general formula (II-a) in which m is 2 and R ¹ -R ⁴ and R ⁶ have two groups connected together has, for example, the formula (II-a' ) represented by the compound.

In formula (II-a'), M, A, R ¹ -R ⁴ , R ⁶ , n and X are the same as M, A, R ¹ -R ⁴ , R ⁶ , n and X in general formula (I). have the same meaning, and R ^1' -R ^4' and R ^6' have the same meaning as R ¹ -R ¹ and R ⁶ .

A' may be the same as or different from A, and is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^6' .

Y is a linking group or a single bond for connecting at least one group selected from R ¹ -R ⁴ and R ⁶ with at least one group selected from R ^1' -R ^4' , R ^6' , It has the same meaning as Y in formula (I-a').

Examples of transition metal compounds represented by formula (II-a') are described below, but are not limited to these compounds.

In the following examples, M has the same meaning as M in formula (II-a).

X has the same meaning as X in formula (II-a), for example, halogen such as Cl or Br, or alkyl such as methyl, but not limited to these groups. When there are a plurality of Xs, they may be the same or different.

n has the same meaning as n in the formula (II-a), which is determined by the valence of the metal M. For example, when two monovalent anions are attached to the metal, n=0 in the case of divalent metals, n=1 in the case of trivalent metals, n=2 in the case of tetravalent metals, n=2 in the case of pentavalent metals In the case of n=3. More specifically, n=2 in the case of Ti(IV), n=2 in the case of Zr(IV), and n=2 in the case of Hf(IV).

In the following examples, Me means methyl, Et means ethyl, iPr means isopropyl, tBu means t-butyl and Ph means phenyl.

The production of the transition metal compound represented by formula (II-a) is not limited in any way, for example, the following method can be used.

Compounds (ligand precursors) that become ligands for constituting transition metal compounds, such as β-diketone compounds, β-ketoester compounds (including thioketones and thioketone esters), or acetylacetonate compounds are commercially available or Prepared by known methods described in the literature.

The above-mentioned compounds, such as acetylacetonate compound and formula R ¹ -NH ₂ (R ¹ has the same meaning as R ¹ in formula (II-a)) such as aniline compound or alkylamine compound) primary amine compound can be reacted to obtain Ligand precursor. More specifically, both starting compounds are dissolved in a solvent. As the solvent, any solvent generally used for this reaction can be used. In particular, alcohol solvents such as methanol or ethanol, or hydrocarbon solvents such as toluene are preferred. Next, the resulting solution is stirred at room temperature to reflux for about 1-48 hours, thereby obtaining the corresponding ligand in high yield.

In the synthesis of the ligand compound, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid can be used as a catalyst. The use of dehydrating agents (such as molecular sieves, magnesium sulfate and sodium sulfate) or the use of Dean and Stark method for dehydration will facilitate the reaction.

Subsequently, the ligand thus obtained is reacted with a transition metal M-containing compound to synthesize the corresponding transition metal compound. More specifically, the synthesized ligands are dissolved in a solvent. The resulting solution can be contacted with a base, if necessary, to prepare a salt. The solution or salt is then mixed with a metal compound (such as a metal halide or metal alkyl) at low temperature, stirred or refluxed at a temperature ranging from -78°C to room temperature for 1-48 hours. As the solvent, any solvent generally used for this reaction can be used. In particular, polar solvents such as diethyl ether or THF or hydrocarbon solvents such as toluene are preferred. Examples of the base used to prepare the phenoxide include metal salts such as lithium salts (eg, n-butyllithium) and sodium salts (eg, sodium hydride) and organic bases such as triethylamine and pyridine, but are not limited to these bases.

Depending on the nature of the compound, the ligand can be directly reacted with the metal compound without preparing a salt, thereby synthesizing the corresponding transition metal compound.

The metal M in the synthesized transition metal compound can also be exchanged with another transition metal by conventional methods. When any of R ¹ -R ⁵ is hydrogen, non-hydrogen substituents may be introduced at any stage of the synthetic steps.

In the transition metal compound represented by general formula (II-a), two or more groups among R ¹ -R ⁴ and R ⁶ may be linked together to form a ring structure. The compounds in which two or more groups (such as R ³ and R ⁴ ) in the R ¹ -R ⁴ and R ⁶ groups are linked together to form an aromatic ring include, for example, compounds represented by the following formula (II-b):

In formula (II-b), N---M generally refers to a dative bond, but in the present invention, it may refer to a dative bond or no dative bond.

In the above general formula, M, m, A, R ¹ , R ² , R ⁶ , n and X and M, m, A, R ¹ , R ² , R ⁶ , n and X in the general formula (II) have the same meaning.

When m is 1, A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent ^R6 , and when m is 2 or more, multiple A groups can be the same or different, and they are respectively an oxygen atom, a sulfur atom , a selenium atom or a nitrogen atom with a substituent ^R6 , and at least one A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent ^R6 .

In the compound represented by formula (II-b), when m is 2 or more, the plurality of A groups are preferably the same, sulfur atom, selenium atom or nitrogen atom with substituent R ⁶ .

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴ and R ⁶ in the general formula (II),

R ¹ , R ² and R ⁶ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be the same or different, and a group of R ¹ , R ² , R 6 -R 10 included in one ligand may be the same as a group of R ⁶ -R ¹⁰ included in another ligand R ¹ , R ² , and R ⁶ -R ¹⁰ are connected.

M is 2 and two of R ¹ , R ² and R ⁷ -R ¹⁰ (or when A is -N(R ⁶ )-, R ¹ , R ² and R ⁶ -R ¹⁰ ) are linked together The transition metal compound represented by the general formula (II-b) forming a ring is, for example, a compound represented by the following general formula (II-b').

In the above general formula, M, R ¹ , R ² , R ⁶ -R ¹⁰ , n and X and M, R ¹ , R ² , R ⁶ -R ¹⁰ , n and X in the general formula (II-b) have the same meaning.

A is a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ⁶ .

A' may be the same as or different from A, and is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^6' .

R ^1' , R ^2' and R ^6' -R ^10' may be the same or different, and have the same meanings as R ¹ , R ² and R ⁶ -R ¹⁰ . Two or more of them, preferably adjacent groups, can be connected to each other to form an alicyclic ring, aromatic ring or hydrocarbon ring with heteroatoms (such as nitrogen).

Y is a linking group or a single bond for linking at least one group selected from R ¹ , R ² and R ⁶ -R ¹⁰ with at least one group selected from R ^1' , R ^2' and R ^6' -R ^10' The groups are connected together, and it has the same meaning as Y in formula (I-a').

Examples of transition metal compounds represented by formula (II-b) are described below, but are not limited to these compounds.

In the following examples, M has the same meaning as M in formula (II-b), such as Sc(III), Ti(III), Ti(IV), Zr(III), Zr(IV), Hf( IV), V(IV), Nb(V), Ta(V), Co(II), Co(III), Ni(II), Rh(II), Rh(III), Rh(IV) or Pd( II), Pd(VI), but not limited to these atoms. in. Preferred is Ti(IV), Zr(IV) or Hf(IV).

X has the same meaning as X in formula (II-b), for example, halogen such as Cl or Br, or alkyl such as methyl, but not limited to these groups. When there are a plurality of Xs, they may be the same or different.

n has the same meaning as n in the formula (II-b), which is determined by the valence of the metal M. For example, when two monovalent anions are attached to the metal, n=0 in the case of divalent metals, n=1 in the case of trivalent metals, n=2 in the case of tetravalent metals, n=2 in the case of pentavalent metals In the case of n=3. More specifically, n=2 in the case of Ti(IV), n=2 in the case of Zr(IV), and n=2 in the case of Hf(IV).

More specifically, the following compounds may be mentioned:

Mention may also be made of compounds in which M, X and n have the same meanings as M, X and n in formula (II-b).

In the above examples, Et refers to ethyl, iPr refers to isopropyl, tBu refers to tert-butyl, Ph refers to phenyl.

A common method for synthesizing the transition metal compound represented by formula (II-b) is described below, but the synthesis method is not limited to this method.

The transition metal compound represented by the formula (II-b) can be synthesized by reacting a compound (ligand precursor) for forming a ligand, such as a thiosalicylidene ligand or an anilino ligand, with a metal compound .

The compound used to form the thiosalicylidene ligand is prepared, for example, by reacting a thiosalicylaldehyde compound with an aniline compound or an amine compound.

Ligand precursors can be prepared by reacting o-acylthiophenols (including the above-mentioned compounds) with aniline compounds or amine compounds.

More specifically, the ligand precursor can be prepared by dissolving thiosalicylaldehyde compound or o-acylthiophenol and aniline compound or primary amine compound with no substituent on the nitrogen part in a solvent, at room temperature to reflux The solution is stirred under conditions for about 1-48 hours. As the solvent, an alcohol solvent such as methanol or ethanol, or a hydrocarbon solvent such as toluene is preferably used. But not limited to these solvents. As the catalyst, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid can be used. Removal of water from the reaction system using the Dean and Stark method is also beneficial to the reaction. Dehydrating agents such as molecular sieves, magnesium sulfate and sodium sulfate can be used.

O-acylthiophenols suitable for use in the present invention can be prepared, for example, by treating the OH group of an o-acylphenol with dimethylthiocarbamate to obtain a thiocarbamate derivative, which is subsequently heated , so that oxygen atoms and sulfur atoms are exchanged.

Anilino ligands are prepared by reacting o-formaniline compounds with aniline compounds or amine compounds. Ligand precursors can be prepared by reacting o-anilines (including the above-mentioned compounds) with aniline compounds or amine compounds. More specifically, the method described above can be used to synthesize o-aniline compounds with no substituents on the nitrogen portion or o-aniline compounds without substituents on the nitrogen portion and aniline compounds or primary amine compounds without substituents on the nitrogen portion. Ligands.

Anilides suitable for use in the present invention can be prepared, for example, by reducing the carboxylic acid group of an anthranilic acid compound. The N-alkylation reaction of anthracene compounds can also be carried out to obtain the corresponding N-alkyl-o-anilide compounds.

Subsequently, the ligand precursor thus obtained is reacted with a metal compound to synthesize a corresponding transition metal compound. More specifically, the ligand compound is dissolved in a solvent. If necessary, the resulting solution can be contacted with a base to obtain a thiophenate or aniline salt. The solution or salt is then mixed with a metal compound (such as a metal halide or metal alkyl) at low temperature, stirred or refluxed at a temperature ranging from -78°C to room temperature for 1-24 hours to prepare a transition metal compound.

Examples of solvents preferably used in the present invention include polar solvents such as diethyl ether and tetrahydrofuran and hydrocarbon solvents such as toluene, but are not limited to these solvents. Examples of bases preferably used in the present invention include lithium salts such as n-butyllithium; sodium salts such as sodium hydride, and nitrogen-containing compounds such as pyridine and triethylamine, but are not limited to these bases.

Depending on the transition metal compound, the ligand compound can be directly reacted with the metal compound without preparing thiophenate or aniline salt to synthesize the corresponding transition metal compound.

The structure of the transition metal compound obtained can be obtained by 270MHz ¹ H-NMR (GSH-270 type, Japan Electron Optics Laboratory), FT-IR (FT-IR 8200D, SHIMADZU), FD-mass spectrometry (SX-102A, Japan Electron Optics laboratory), metal content analysis (dissolved in dilute nitric acid after dry ashing, and analyzed by ICP method, instrument: SHIMAZDU ICPS-8000) and carbon, hydrogen and nitrogen content analysis (Helaus, CHNO type).

In the transition metal compound (A-2) represented by the general formula (II), Q is a nitrogen atom and R ³ and R ⁴ are connected together to form an aromatic ring compound can be represented by the following formula (II-c):

In the above general formula, N---M generally refers to a coordinate bond, but compounds without such a coordinate bond are also included in the present invention.

In the above formula, M, m, A, R ¹ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ⁶ , n and X in the general formula (II).

R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴¹ and R ⁶ in the general formula (II),

R ¹ and R ⁶ -R ¹⁰ may be the same or different, and two or more of them may be connected to each other to form a ring.

When m is 2 or greater, a plurality of R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be the same or different, and a group of R ¹ , R ⁶ -R contained in one ligand ¹⁰ may be linked to a set of R ¹ , R ⁶ -R ¹⁰ contained in another ligand.

M is 2 and a set of R ¹ and R ⁶ -R ¹⁰ groups contained in one ligand is linked together with a set of R ¹ and R ⁶ -R ¹⁰ groups contained in another ligand The transition metal compound represented by the general formula (II-c) is, for example, a compound represented by the following general formula (II-c').

In general formula (II-c') ^, M, ^A , R ¹ , ^{R 6 -R 10} and X have The same meaning, R ^1' , R ^6' -R ^10' and R ¹ , R ⁶ -R ¹⁰ have the same meaning.

A' may be the same as or different from A, and is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^6' .

R ¹ and R ⁶ -R ¹⁰ may be the same as or different from R ^1' and R ^6' -R ^10' .

Y is a linking group or a single bond for connecting at least one group selected from R ¹ and R ⁶ -R ¹⁰ with at least one group selected from R ^1' and R ^6' -R ^10' , It has the same meaning as Y in formula (I-a').

Examples of transition metal compounds represented by formula (II-c) are described below, but are not limited to these compounds.

In the following examples, M has the same meaning as M in the general formula (II-C).

X has the same meaning as X in formula (II-c), for example, halogen such as Cl or Br, or alkyl such as methyl, but not limited to these groups. When there are a plurality of Xs, they may be the same or different.

n has the same meaning as n in the formula (II-c), which is determined by the valence of the metal M. For example, when two monovalent anions are attached to the metal, n=0 in the case of divalent metals, n=1 in the case of trivalent metals, n=2 in the case of tetravalent metals, n=2 in the case of pentavalent metals In the case of n=3. More specifically, n=2 in the case of Ti(IV), n=2 in the case of Zr(IV), and n=2 in the case of Hf(IV).

In the following examples, Me means methyl, Et means ethyl, iPr means isopropyl, tBu means t-butyl, Ph means phenyl.

The preparation of the transition metal compound represented by formula (II-c) is not limited in any way, for example, it can be prepared by the same method as the transition metal compound represented by formula (I-c) above.

Depending on the nature of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without preparing a phenoxide. For example, the following compounds are reacted with a base to form a salt, which is then reacted with a transition metal halide to prepare the corresponding transition metal compound.

As the olefin polymerization catalyst, the above transition metal compounds (A-1) and (A-2) may be used alone or in combination of two or more, or in combination with other transition metal compounds.

Examples of other transition metal compounds include known transition metal compounds containing ligands of heteroatoms such as nitrogen, oxygen, sulfur, boron or phosphorus.

Other transition metal compounds

Examples of transition metal compounds suitable for use in the present invention as non-transition metal compounds (A-1) and (A-2) include the following compounds:

(1) A transition metal imide compound represented by the following formula:

In the above general formula, M is a transition metal atom of Group 8-10 of the periodic table, preferably nickel, palladium or platinum.

R ²¹ -R ²⁴ may be the same or different, and are hydrocarbon groups containing 1-50 carbon atoms, halogenated hydrocarbon groups containing 1-50 carbon atoms, hydrocarbon-substituted silyl groups, or silyl groups containing nitrogen, oxygen, A hydrocarbon group substituted with a substituent of at least one element selected from phosphorus, sulfur and silicon.

Two or more groups (preferably adjacent groups) among R ²¹ -R ²⁴ may combine with each other to form a ring.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. q is an integer of 0-4. When q is 2 or greater, the multiple X groups may be the same or different.

(2) Transition metal amide compounds represented by the following formula:

In the above formula, M is a transition metal atom of Group 3-6 of the periodic table, preferably titanium, zirconium or hafnium.

R' and R" can be the same or different, and are hydrogen atoms, hydrocarbon groups containing 1-50 carbon atoms, halogenated hydrocarbon groups containing 1-50 carbon atoms, hydrocarbon-substituted silyl groups, or containing at least one selected from Substituents for the elements nitrogen, oxygen, phosphorus, sulfur and silicon.

A is an atom of Group 13-16 of the periodic table, specifically boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, tin, etc., preferably carbon or silicon.

m is an integer of 0 or 2. n is an integer of 1-5. When n is 2 or more, a plurality of A atoms may be the same or different.

E is a substituent containing at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, the two E's may be the same or different, or may combine with each other to form a ring.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. p is an integer of 0-4. When p is 2 or greater, the multiple X groups may be the same or different.

X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group.

(3) Transition metal diphenoxy compounds represented by the following formula:

In the above formula, M is a transition metal atom of Group 3-11 of the periodic table;

l and m are integers of 0 or 1 respectively;

A and A' are hydrocarbon groups containing 1-50 carbon atoms, halogenated hydrocarbon groups containing 1-50 carbon atoms, or hydrocarbon groups containing 1-50 carbon atoms with substituents containing oxygen, sulfur or silicon, or In halogenated hydrocarbon groups, A and A' may be the same or different.

B is a hydrocarbon group having 0 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a group represented by R ¹ R ² Z, oxygen or sulfur. R and R are ^respectively a hydrocarbon group containing 1-20 carbon atoms or a hydrocarbon group containing at least one heteroatom with 1-20 carbon atoms ^, and Z is a carbon atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom.

n is a number satisfying the valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When n is 2 or more, a plurality of X groups may be the same or different, or may be combined with each other to form a ring.

(4) A transition metal compound represented by the following formula, which comprises a ligand having a cyclopentadienyl skeleton containing at least one heteroatom:

In the above formula, M is a transition metal atom of Groups 3-11 of the periodic table.

X is an atom of Group 13, Group 14 or Group 15 of the periodic table, and at least one X is an element other than carbon.

Each R may be the same or different, and is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon. Substituted Hydrocarbyl. Two or more R can be combined with each other to form a ring.

a is 0 or 1, b is an integer of 1-4, when b is 2 or more, the [((R) _a ) ₅ -X ₅ ] groups can be the same or different, and multiple R can be bridged to each other.

c is a number satisfying the valence of M.

Y is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, when c is 2 or larger, multiple Y groups can be the same or different, and can combine with each other to form a ring.

(5) A transition metal compound represented by the formula PB(Pz) ₃ MX _n :

In the above formula, M is a transition metal atom of Group 3-11 of the periodic table; R is a hydrogen atom, a hydrocarbon group containing 1-20 carbon atoms or a halogenated hydrocarbon group containing 1-20 carbon atoms; Pz is pyrazole or substituted pyrazolyl.

n is a number satisfying the valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, when n is 2 or larger, multiple groups may be the same or different, or may combine with each other to form a ring.

(6) A transition metal compound represented by the following formula:

In the above formula, Y ¹ and Y ³ can be the same or different, and they are elements of group 15 of the periodic table; Y ² is an element of group 16 of the periodic table.

R ²¹ -R ²⁸ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups containing 1-20 carbon atoms, halogenated hydrocarbon groups containing 1-20 carbon atoms, oxygen-containing, sulfur-containing groups or silicon-containing groups groups, two or more of them can combine with each other to form a ring.

(7) A compound comprising a compound represented by the following formula and a transition metal atom from Group 8-10 of the periodic table:

In the above formula, R ³¹ -R ³⁴ may be the same or different, and are respectively hydrogen atoms, halogen atoms, hydrocarbon groups containing 1-20 carbon atoms, or halogenated hydrocarbon groups containing 1-20 carbon atoms, two of them One or more can be combined with each other to form a ring.

(8) A transition metal compound represented by the following formula:

In the above formula, M is a transition metal atom of Groups 3-11 of the periodic table.

m is an integer of 0-3, n is an integer of 0 or 1, p is an integer of 1-3, and q is a number satisfying the valence of M.

R ⁴¹ -R ⁴⁸ can be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group containing 1-20 carbon atoms, halogenated hydrocarbon group containing 1-20 carbon atoms, oxygen-containing group, sulfur-containing group, silicon-containing group group or nitrogen-containing group, two or more of them can combine with each other to form a ring.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms, a halogenated hydrocarbon group containing 1-20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When q is 2 or more, a plurality of X groups may be the same or different, or may be combined with each other to form a ring.

Y is a group bridging a boron-containing benzene ring (boratabenzene ring), and is carbon, silicon or germanium.

A is an element of Group 14, Group 15 or Group 16 of the periodic table.

(9) A transition metal compound other than the above compound (4) and containing a ligand having a cyclopentadienyl skeleton.

(10) A compound containing magnesium, titanium and halogen as main components.

The olefin polymerization catalyst of the present invention comprises a transition metal compound (A-1) or (A-2), which may also optionally comprise at least one compound (B), the compound (B) being selected from:

(B-1) organometallic compounds;

(B-2) organoaluminoxy compounds; and

(B-3) A compound that reacts with the transition metal compound (A-1) or (A-2) to form an ion pair.

Next, various compounds of component (B) will be described.

(B-1) Organometallic compounds

Examples of the organometallic compound (B-1) optionally used in the present invention include organometallic compounds containing metals of Group 1, Group 2, Group 12 and Group 13 of the periodic table, such as the compounds described below.

(B-1a) An organoaluminum compound represented by the following formula:

R ^a _m Al(OR ^b ) _n H _p X _q

Wherein, R ^a and R ^b can be the same or different, respectively containing 1-15 carbon atoms, preferably hydrocarbon groups containing 1-4 carbon atoms; X is a halogen atom; <m≤3, 0≤n<3, 0≤p<3, 0≤q<3 and m+n+p+q=3.

(B-1b) An alkyl coordination compound comprising a Group 1 metal and aluminum represented by the following formula:

M ² AlR ^a ₄

Wherein, M ² is Li, Na or K; R ^a is a hydrocarbon group containing 1-15 carbon atoms, preferably 1-4 carbon atoms.

(B-1c) A dialkyl compound containing a Group 2 or Group 12 metal represented by the following formula:

R ^a R ^b M ³

Wherein, R ^a and R ^b may be the same or different, and are respectively hydrocarbon groups containing 1-15 carbon atoms, preferably 1-4 carbon atoms; M ³ is Mg, Zn or Cd.

Examples of organoaluminum compounds (B-1a) include:

An organoaluminum compound represented by the formula:

R ^a _m Al(OR ^b ) _3-m

Among them, R ^a and R ^b can be the same or different, and are respectively hydrocarbon groups containing 1-15 carbon atoms, preferably 1-4 carbon atoms; m is preferably a number satisfying the condition 1.5≤m≤3;

An organoaluminum compound represented by the formula:

R ^a _m AlX _3-m

Wherein, R ^{is a} hydrocarbon group containing 1-15 carbon atoms, preferably 1-4 carbon atoms; X is a halogen atom; m is preferably a number satisfying the condition 0<m<3;

An organoaluminum compound represented by the formula:

R ^a _m AlH _3-m

Wherein, R ^is a hydrocarbon group containing 1-15 carbon atoms, preferably 1-4 carbon atoms; m is preferably a number satisfying the condition 2≤m<3;

as well as

An organoaluminum compound represented by the formula:

R ^a _m Al(OR ^b ) _n X _q

Wherein, R ^a and R ^b can be the same or different, and are respectively a hydrocarbon group containing 1-15 carbon atoms, preferably 1-4 carbon atoms; X is a halogen atom; m, n and q satisfy the condition 0<m ≤3, 0≤n<3, 0≤q<3 and m+n+q=3.

Specific examples of the organoaluminum compound (B-1a) include:

Tri-n-alkylaluminum, such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum;

Branched-chain trialkylaluminum, such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tris(2-methylbutyl)aluminum, tris(3-methyl Butyl)aluminum, tris(2-methylpentyl)aluminum, tris(3-methylpentyl)aluminum, tris(4-methylpentyl)aluminum, tris(2-methylhexyl)aluminum, tri( 3-methylhexyl)aluminum and tris(2-ethylhexyl)aluminum;

Tricycloalkylaluminum, such as tricyclohexylaluminum and tricyclooctylaluminum;

Aluminum triaryls such as triphenylaluminum and tricresylaluminum;

Dialkylaluminum hydrides such as diisobutylaluminum hydride and diisobutylaluminum hydride;

Trienyl aluminum, such as trienyl aluminum represented by the formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers, and z≥2x), such as iso Aluminum pentadienyl;

Dialkoxyalkylaluminum, such as dimethoxyisobutylaluminum, diethoxyisobutylaluminum and diisopropoxyisobutylaluminum;

Alkoxydialkylaluminum, such as methoxydimethylaluminum, ethoxydiethylaluminum and butoxydibutylaluminum;

Sesquialkoxyalkylaluminum, such as sesquiethoxyethylaluminum and sesquibutoxybutylaluminum;

Partially alkoxylated aluminum alkyls, such as aluminum alkyls having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 ;

Aryloxydialkylaluminum, such as phenoxydiethylaluminum, (2,6-di-tert-butyl-4-methylphenoxy)diethylaluminum, bis(2,6-di-tert-butyl -4-methylphenoxy)ethylaluminum, (2,6-di-tert-butyl-4-methylphenoxy)diisobutylaluminum and bis(2,6-di-tert-butyl-4- Methylphenoxy) isobutylaluminum;

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;

Alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide;

Partially halogenated alkylaluminum such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide;

Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;

Partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride and propylaluminum dihydride; and

Partially alkoxylated and halogenated aluminum alkyls such as ethoxyethylaluminum chloride, butoxybutylaluminum chloride and ethoxyethylaluminum bromide.

Compounds similar to the organoaluminum compound (B-1a) can also be used. For example, an organoaluminum compound in which two or more aluminum compounds are bonded together through a nitrogen atom, such as (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ .

Examples of the compound (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

Other compounds can also be used as the organometallic compound (B-1), which include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide , ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium and butylethylmagnesium magnesium.

Mixtures of compounds capable of producing the above-mentioned organoaluminum compounds in a polymerization system, such as mixtures of aluminum halides and alkyllithiums, and mixtures of aluminum halides and alkylmagnesiums may also be used.

Among the above organometallic compounds (B-1), organoaluminum compounds are preferred.

The organometallic compound (B-1) may be used alone or in combination of two or more.

(B-2) Organoaluminum oxy compounds

The organoaluminum oxy compound (B-2) optionally used in the present invention may be a conventional aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in Japanese Patent Laid-Open No. 78687/1990.

Conventional aluminoxanes can be prepared, for example, by the following methods, and are generally obtained as solutions in hydrocarbon solvents.

(1) Adding an organic aluminum compound (such as trialkylaluminum) to a compound containing absorbed water or a salt containing crystal water (such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerium trichloride hydrate) In the hydrocarbon medium suspension, the organoaluminum compound is reacted with adsorbed water or crystal water.

(2) In a medium (such as benzene, toluene, ether or tetrahydrofuran), let water, ice or water vapor directly act on the organoaluminum compound (such as trialkylaluminum).

(3) Reaction of an organotin oxide (such as dimethyltin oxide or dibutyltin oxide) with an organoaluminum compound (such as trialkylaluminum) in a medium (such as decane, benzene or toluene).

Aluminoxanes may contain small amounts of organometallic components. Alternatively, the solvent or unreacted organoaluminum compound may be distilled off from the recovered aluminoxane solution, and the residue may be redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Examples of the organoaluminum compound used in the production of aluminoxane include the same organoaluminum compounds as the aforementioned organoaluminum compound (B-1a). Among them, trialkylaluminum and tricycloalkylaluminum are preferable. Particularly preferred is trimethylaluminum.

The organoaluminum compounds may be used alone or in combination of two or more.

Examples of solvents used in the manufacture of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and methyl cumene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane , decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and gas oil; And the halogenated products of these aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (such as their chlorinated products and brominated products). Ethers such as diethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are preferred.

The benzene-insoluble organoaluminum oxy-compound used in the present invention preferably contains an Al component that can be dissolved in benzene at 60°C, usually no more than 10%, preferably no more than 5%, particularly preferably no more than 2% (calculated by Al atoms) ) of organoaluminum oxy compounds. That is, the organoaluminum oxy compound which is insoluble in benzene is preferably insoluble in benzene or slightly soluble in benzene.

The organoaluminum oxy compound used in the present invention is, for example, a boron-containing organoaluminum oxy compound represented by the following formula (IV):

Wherein R ²⁰ is a hydrocarbon group containing 1-10 carbon atoms; each R ²¹ can be the same or different, and is a hydrogen atom, a halogen atom or a hydrocarbon group containing 1-10 carbon atoms.

The boron-containing organoaluminum compound represented by formula (IV) can be obtained by reacting an alkylboronic acid represented by formula (V) with an organoaluminum compound at a temperature from -80° C. to room temperature in an inert solvent under an inert gas atmosphere. Minutes to 24 hours and make, the alkyl boronic acid of described formula (V) is as follows:

R ²⁰ -B-(OH) ₂ (v)

Wherein R ²⁰ is the same group as described above.

Examples of the alkyl boronic acid represented by the formula (V) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boronic acid, cyclohexyl boronic acid, Phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis(trifluoromethyl)phenylboronic acid. Among them, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred.

These alkylboronic acids may be used alone or in combination of two or more.

Examples of the organoaluminum compound reacted with the alkylboronic acid include the same organoaluminum compounds as the aforementioned organoaluminum compound (B-1a). Among them, trialkylaluminum and tricycloalkylaluminum are preferred. Particularly preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum. These organoaluminum compounds may be used alone or in combination of two or more.

The above organoaluminum oxy compounds (B-2) may be used alone or in combination of two or more.

(B-3) A compound that reacts with the transition residue compound (A) to form an ion pair

The compound (B-3) (hereinafter referred to as "ionizing ionic compound") that can optionally be used in the present invention to form an ion pair by reacting with a transition metal compound is a ) react to form ion pairs. That is, any compound capable of forming an ion pair by contact with the transition metal compound (A-1) or (A-2) can be used as the compound (B-3).

Examples of these compounds include Lewis acids, ionic compounds, borane compounds, and carborane compounds, descriptions of which can be found in Japanese Patent Laid-Open No. 501950/1989, No. 502036/1989, No. 179005/1991, No. 179006/1991 , No. 207703/1991 and No. 207704/1991 and US Patent No. 5,321,106. Heteropoly compounds or isopoly compounds may also be used.

The Lewis acid is, for example, a compound represented by BR ₃ (R is fluorine or phenyl which may contain a substituent such as fluorine, methyl, trifluoromethyl). Examples of such compounds include boron trifluoride, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron , tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron and tris(3,5-dimethylphenyl)boron.

The ionic compound is, for example, a compound represented by the following formula (VI):

In the above formula, R ²² is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, a ferrocenium cation having a transition metal, or the like.

R ²³ -R ²⁶ may be the same or different, and they are organic groups, preferably aryl or substituted aryl.

Examples of carbenium cations include: trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation and tris(dimethylphenyl)carbenium cation.

Examples of ammonium cations include: trialkylammonium cations such as trimethylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations and tri(n-butyl)ammonium cations; N,N- Dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium cation; dialkyl Ammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

Examples of phosphonium cations include: triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation and tris(dimethylphenyl)phosphonium cation.

R ²² is preferably a carbonium cation or an ammonium cation, particularly preferably a triphenylcarbenium cation, N,N-dimethylanilinium cation or N,N-diethylanilinium cation.

Trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts or triarylphosphonium salts can also be used as ionic compounds.

Examples of trialkyl-substituted ammonium salts include: triethylammonium tetraphenylboride, tripropylammonium tetraphenylboride, tri-n-butylammonium tetraphenylboride, trimethyl-tetraphenylboride Ammonium trimethyl ammonium, tetra-o-tolyl boride trimethyl ammonium, tetrakis (pentafluorophenyl) tri-n-butyl ammonium boride, tetrakis (o, p-xylyl) tripropyl ammonium boride, tetrakis (m-, m- -Xylyl)tri-n-butylammonium boride, tetrakis(p-trifluoromethylphenyl)tri-n-butylammonium boride, tetrakis(3,5-bis(trifluoromethyl)phenyl)tri-n-butylammonium boride n-Butylammonium and tri-n-butylammonium tetra-o-tolyl boride.

Examples of N,N-dialkylanilinium salts include: N, N-dimethylanilinium tetraphenylboride, N, N-diethylanilinium tetraphenylboride and N tetraphenylboride , N-2,4,6-pentamethylanilinium.

Examples of dialkylammonium salts include di(1-propyl)ammonium tetrakis(pentafluorophenyl)boride and dicyclohexylammonium tetraphenylboride.

Also available as ionic compounds: tetrakis (pentafluorophenyl) borate triphenylcarbenium, tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate dichloro Ironium, pentaphenylcyclopentadienyl triphenylcarbenium complex, pentaphenylcyclopentadienyl N,N-diethylanilinium complex, and boron compound represented by the following formula (VII) :

Wherein, Et is ethyl, or the compound represented by formula (VIII),

Examples of the borane compounds include:

Decaborane (14);

Anionic salts, such as bis(tri-n-butylammonium)nonaborate, di(tri-n-butylammonium)decaborate, di(tri-n-butylammonium)undecaborate, bis(tri-n-butylammonium)dodecaborate, Di(tri-n-butylammonium) decachlorodecaborate and di(tri-n-butylammonium) dodecachlorododecaborate; and

Metal borane anion salts such as tri-n-butylammonium bis(dodecahydrododecaborate) cobalt(III) acid and bis[tri-n-butylamine] bis(dodecahydrododecaborate)nickel(III) acid.

Examples of carborane compounds include:

Anionic salts, such as 4-carbasuborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydro-1-benzene Base-1,3-dicarbononaborane, dodecahydro-1-methyl-1,3-dicarbononaborane, undecahydro-1,3-dimethyl-1,3-di Carbononaborane, 7,8-Dicabororane (13), 2,7-Dicaborane (13), Undecahydro-7,8-Dimethyl-7, 8-Dicarba-undecaborane, Dodecahydro-11-methyl-2,7-dicarba-undecaborane, 1-carba-decaborate tri-n-butylammonium, 1-carba-undecaborate Tri-n-butylammonium, tri-n-butylammonium 1-carbon dodecaborate, tri-n-butylammonium 1-trimethylsilyl-1-carbodedecaborate, tri-n-butylammonium bromo-1-carbodecaborate n-Butylammonium, 6-carbon decanoboric acid (14) tri-n-butyl ammonium, 6-carbon decanoboric acid (12) tri-n-butyl ammonium, 7-carbon undecaboric acid (13) tri-n-butyl ammonium , 7,8-dicarbonated undecaneboronic acid (12) tri-n-butylammonium, 2,9-dicarbonated undecaneboric acid (12) tri-n-butylammonium, dodecahydro-8-methyl-7 , Tri-n-butylammonium 9-dicarbonate undedecaborate, undecahydro-8-ethyl-7,9-tri-n-butylammonium dicarbonate undecaborate, undecahydro-8-butyl-7 , Tri-n-butylammonium 9-dicarbonate undedecaborate, undecahydro-8-allyl-7,9-tri-n-butylammonium dicarbonate undedecaborate, undecahydro-9-trimethyl Tri-n-butylammonium silyl-7,8-dicarbaundecaborate and tri-n-butylammonium undecahydro-4,6-dibromo-7-carbaundecaborate; and

Salts of metal carborane anions, such as

Tri-n-butylammonium bis(nonahydro-1,3-dicarbononylboronate)cobalt(III),

Di(undecahydro-7,8-dicarboboronic acid) tri-n-butylammonium ferrate(III),

Tri-n-butylammonium bis(undecahydro-7,8-dicarbonate undecaborate)cobalt(III),

Tri-n-butylammonium di(undecahydro-7,8-dicarbonated undedecaborate)nickel(III),

Tri-n-butylammonium bis(undecahydro-7,8-dicarboboronate)copper(III),

Tri-n-butylammonium di(undecahydro-7,8-dicarboboronate) gold(III),

Tri-n-butylammonium bis(nonahydro-7,8-dimethyl-7,8-dicarboboronic acid)ferrate(III),

Tri-n-butylammonium bis(nonahydro-7,8-dimethyl-7,8-dicarboboronic acid) chromium(III),

Tri-n-butylammonium bis(tribromooctahydro-7,8-dicarbonate undecaborate)cobalt(III),

Bis(undecahydro-7-carbon undedecaborate) chromium(III) tris[tri(n-butyl)ammonium],

Bis(undecahydro-7-carbon undedecaborate) manganese(IV) acid bis[tri(n-butyl)ammonium],

di(tri(n-butyl)ammonium bis(undecahydro-7-carbaboronate)cobalt(III)ate), and

Bis(undecahydro-7-carbaboronic acid)nickel(IV) acid bis[tri(n-butyl)ammonium].

The heteropoly compound contains one atom of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Examples of these compounds include: phosphovanadate, germanovanadate, arsenovanadate, phosphoniobate, germanium niobate, silicomomolybdate, phosphomolybdate, titanium molybdate, germanium molybdate, arsenomolybdate, tin molybdate, Phosphotungstic acid, germanium tungstic acid, tin tungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanium tungstovanadate, phosphomolybdotungstovanadate, germanium molybdenum tungstovanadate, phosphomolybdenum tungstic acid, and phosphomolybdovanadate, and salts of these acids, for example salts of these acids with metals of Group I or II of the Periodic Table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium or barium, organic salts of the abovementioned acids (such as triphenylethyl salt), and isopoly compounds, but not limited thereto.

These heteropoly compounds and isopoly compounds may be used alone or in combination of two or more, respectively.

The above ionizing ionic compounds (B-3) may be used alone or in combination of two or more.

When the transition metal compound (A-1) or (A-2) is used as a catalyst, a high molecular weight olefin polymer can be obtained with high polymerization activity. If an organoaluminum oxy compound (B-2) such as methylaluminoxane is used in combination as a cocatalyst, the catalyst shows extremely high polymerization activity for olefinic compounds. When the ionizing ionic compound (B-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used as a cocatalyst component, an olefin polymer having an extremely high molecular weight can be obtained with excellent activity.

In the olefin polymerization catalyst of the present invention, in addition to the above-mentioned transition metal compound (A-1) or (A-2) and In addition to at least one compound (B) of (B-3), the following carrier (C) may optionally be used.

(C) carrier

The carrier (C) optionally used in the present invention is an inorganic or organic compound in granular or granular solid form. Preferred inorganic compounds include porous oxides, inorganic chlorides, clays, clay minerals or ion exchange layered compounds.

Examples of porous oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , and complexes or mixtures containing these oxides, such as natural or synthetic Zeolite _{, SiO2} -MgO, _SiO2 - _{Al2O3 , SiO2} - _TiO2 , _SiO2 - _V2O5 , _{SiO2 -Cr2O3 and} SiO2 _{- TiO2} -MgO. Among them, preferred are compounds containing SiO ₂ and/or Al ₂ O ₃ as main components.

Inorganic oxides may contain small amounts of carbonates, sulfates, nitrates and oxide components such as Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) _3. BaSO ₄ , KNO ₃ , Mg(NO ₃ ) ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O or Li ₂ O.

Although the performance of the porous oxide varies with its type and manufacturing method, the particle size of the carrier used in the present invention is preferably 10-300 microns, preferably 20-200 microns, and the specific surface area is preferably 50-1,000 m ² /g, preferably 100-700 ^m2 /g, and the pore volume is 0.3-3.0 ^cm3 /g. If necessary, the carrier can be used after being calcined at 100-1000°C, preferably at 150-700°C.

Examples of inorganic chlorides useful in the present invention include MgCl ₂ , MgBr ₂ , MnCl ₂ and MnBr ₂ . The inorganic chloride may be used as it is, or may be ground into a powder by, for example, ball milling or vibration milling. A fine particulate inorganic chloride obtained by dissolving the inorganic chloride in a solvent such as alcohol followed by precipitation with a precipitating agent can be used.

Clays used as carriers in the present invention generally consist primarily of clay minerals. The ion-exchange layered compound usable as a carrier in the present invention is a compound having a crystal structure in which planes formed by ionic bonds etc. are stacked parallel to each other with weak bonding strength, and contained therein The ions are exchangeable. Most clay minerals are ion-exchanged layered compounds. The clays, clay minerals and ion-exchange layered compounds used in the present invention are not limited to natural ones, but also include synthetic ones.

Examples of such clays, clay minerals and ion-exchanged layered compounds include clays, clay minerals and ionic crystals having a layered crystal structure such as hexagonal closest-packed type, antimony type, _CdCl2 type, and _CdI2 type compound.

Specific examples of clay and clay minerals include kaolin, bentonite, wood knot clay, gairome clay, allophane, ferrosilicate, pyrophyllite, mica, montmorillonite, vermiculite, chlorite, palygorskite, Kaolinite, pearl clay, dickite and halloysite. Specific examples of ion-exchange layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ · 3H ₂ O, α-Ti(HPO ₄ ) ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ- Ti(HPO ₄ ) ₂ and γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O.

For clays, clay minerals, and ion-exchange layered compounds, compounds having a pore volume of not less than 0.1 cc/g as measured by mercury intrusion porosimetry on pores with a radius of not less than 20 angstroms are preferred, particularly preferably the pore volume 0.3-5cc/g compound. Pore volumes were measured by mercury porosimetry on pores with a radius of 20 to 3 x 10 ⁴ angstroms.

When a compound having a pore volume of less than 0.1 cc/g as measured on pores having a radius of not less than 20 angstroms is used as a support, high polymerization activity can hardly be obtained.

Chemical treatments of the clays and clay minerals used in the present invention are also preferred. Any surface treatment may be used, such as treatment to remove impurities adhering to the surface and treatment to affect the crystal structure of the clay. Examples of such chemical treatments include: acid treatment, alkali treatment, salt treatment and organic matter treatment. Acid treatment not only removes impurities from the surface, but also elutes cations (such as Al, Fe, and Mg) present in the crystal structure, thereby increasing the surface area. Alkali treatment can destroy the crystal structure of clay and change the structure of clay. Salt treatment and organic substance treatment can form, for example, ionic complexes, molecular complexes or organic derivatives to change the surface area or interlayer distance.

The ion-exchange layered compound used in the present invention may be a layered compound in which exchangeable ions between layers are exchanged with other bulky ions by utilizing ion exchange properties to increase the interlayer distance. The bulky ions act like pillars to support the layered structure, the ions are often referred to as "pillars". The introduction of other substances between the layers of a layered compound is called "intercalation". Examples of guest compounds that can be intercalated include: cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ (R is a hydrocarbon group, etc.); and metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ and [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ .

The above compounds may be used alone or in combination of two or more.

The intercalation of these compounds can be in the presence of polymers obtained by hydrolysis of metal alkoxides (such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ , where R is a hydrocarbon group, etc.), or in colloidal inorganic in the presence of compounds such as SiO ₂ . Examples of pillars include oxides obtained by intercalating the above-mentioned metal hydroxide ions between layers followed by dehydration by heating.

The above-mentioned clays, clay minerals and ion-exchange layered compounds may be used as they are, or may be used after being subjected to ball milling, sieving or the like. In addition, it can be used after water adsorption or heat dehydration. The clay, clay minerals and ion-exchange layered compounds may be used alone or in combination of two or more.

Among the above materials, clay and clay minerals are preferred, and montmorillonite, vermiculite, hectorite, cupolite and synthetic mica are particularly preferred.

The organic compound is, for example, a granular or granular solid compound with a particle size of 10-300 micrometers. Examples of such compounds include: polymers or Copolymers, polymers or copolymers prepared using vinylcyclohexane or styrene as the main component, and their modified products.

If necessary, in addition to transition metal compound (A-1) or (A-2), selected from organometallic compound (B-1), organoaluminum oxy compound (B-2) and ionizing ionic compound (B-3) In addition to at least one compound (B) and optional support (C), the olefin polymerization catalyst of the present invention may also contain the following specific organic compound (D).

(D) Organic compound components

In the present invention, the organic compound component (D) may be optionally used for improving the polymerization ability and the properties of the resulting polymer. Examples of organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonic acid esters.

As the alcohol and phenol compounds, generally used are compounds represented by the formula R ³¹ —OH, wherein R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. The alcohol is preferably a compound represented by the above formula wherein R ³¹ is a halogenated hydrocarbon group. The phenolic compound is preferably a compound in which the α, α'-positions of the hydroxyl group are substituted by a hydrocarbon group having 1 to 20 carbon atoms.

As carboxylic acids, generally used are compounds represented by the formula R ³² -COOH, wherein R ³² is a hydrocarbon group containing 1-50 carbon atoms or a halogenated hydrocarbon group containing 1-50 carbon atoms, preferably containing 1-50 A halogenated hydrocarbon group of carbon atoms.

As the phosphorus compound, phosphoric acid containing a P-O-H bond, phosphoric acid ester containing a P-OR bond or P=O bond, and a phosphine oxide compound are preferably used.

The sulfonate used in the present invention is a compound represented by the following formula (IX):

In the above formula, M is an element of Groups 1-14 of the periodic table.

R ³³ is hydrogen, a hydrocarbon group containing 1-20 carbon atoms or a halogenated hydrocarbon group containing 1-20 carbon atoms.

X is a hydrogen atom, a halogen atom, a hydrocarbon group containing 1-20 carbon atoms or a halogenated hydrocarbon group containing 1-20 carbon atoms.

m is an integer of 1-7, and 1≤n≤7.

In Fig. 1 and Fig. 2, the preparation method of the olefin polymerization catalyst of the present invention is shown.

Next, the olefin polymerization method will be described.

The olefin polymerization method of the present invention involves polymerizing (copolymerizing) olefins in the presence of the above catalyst.

In the polymerization, any method of using and adding the components and any order of adding the components may be chosen, some examples of which are given below.

(1) The transition metal compound (A-1) or (A-2) (hereinafter simply referred to as "component (A)") is charged into a polymerization reactor.

(2) Component (A) and at least one compound (B) selected from organometallic compounds (B-1), organoaluminum oxide compounds (B-2) and ionizing ionic compounds (B-3) are mixed in any order ) (hereinafter referred to simply as "component (B)") into the polymerization reactor.

(3) The catalyst obtained by precontacting the component (A) and the component (B) is charged into the polymerization reactor.

(4) The catalyst component obtained by previously contacting the component (A) and the component (B) and the component (B) are charged into the polymerization reactor in an arbitrary order. In this case, components (B) may be the same or different.

(5) The catalyst component formed by supporting the component (A) on the carrier (C) and the component (B) are fed into the polymerization reactor in an arbitrary order.

(6) The catalyst formed by supporting the component (A) and the component (B) on the carrier (C) is charged into the polymerization reactor.

(7) The catalyst component supported by the component (A) and the component (B) on the carrier (C) and the component (B) are fed into the polymerization reactor in an arbitrary order. In this case, components (B) may be the same or different.

(8) The catalyst component formed by supporting the component (B) on the carrier (C) and the component (A) are fed into the polymerization reactor in an arbitrary order.

(9) The catalyst component in which the component (B) is supported on the carrier (C), the component (A) and the component (B) are charged into the polymerization reactor in an arbitrary order. In this case, components (B) may be the same or different.

(10) The component in which the component (A) is supported on the carrier (C) and the component in which the component (B) is supported on the carrier (C) are fed into the polymerization reactor in an arbitrary order.

(11) Add the component formed by component (A) supported on the carrier (C), the component formed by component (B) supported on the carrier (C), and component (B) into the polymerization in any order in the reactor. In this case, components (B) may be the same or different.

(12) Component (A), component (B) and organic compound component (D) are charged into the polymerization reactor in an arbitrary order.

(13) The component obtained by contacting the component (B) and the component (D) in advance and the component (A) are charged into the polymerization reactor in an arbitrary order.

(14) The component obtained by loading the component (B) and the component (D) on the carrier (C) and the component (A) are fed into the polymerization reactor in an arbitrary order.

(15) The catalyst component formed by contacting the component (A) and the component (B) in advance and the component (D) are charged into the polymerization reactor in an arbitrary order.

(16) The catalyst component formed by contacting the component (A) and the component (B) in advance, the component (B) and the component (D) are charged into the polymerization reactor in an arbitrary order.

(17) The catalyst component formed by previously contacting component (A) and component (B) and the component formed by previously contacting component (B) and component (D) are fed into the polymerization reactor in an arbitrary order.

(18) The component in which the component (A) is supported on the carrier (C), the component (B) and the component (D) are charged into the polymerization reactor in an arbitrary order.

(19) The component formed by supporting the component (A) on the carrier (C) and the component formed by previously contacting the component (B) with the component (D) are fed into the polymerization reactor in an arbitrary order.

(20) Catalyst components formed by preliminarily contacting component (A), component (B) and component (D) with each other are charged into the polymerization reactor in an arbitrary order.

(21) The catalyst component formed by contacting component (A), component (B) and component (D) with each other beforehand and component (B) are charged into the polymerization reactor in an arbitrary order. In this case, components (B) may be the same or different.

(22) The catalyst formed by supporting the component (A), component (B) and component (D) on the carrier (C) is charged into the polymerization reactor.

(23) The catalyst component formed by supporting the component (A), the component (B) and the component (D) on the carrier (C) and the component (B) are fed into the polymerization reactor in an arbitrary order. In this case, components (B) may be the same or different.

Prepolymerization of olefins can be carried out on a solid catalyst component in which component (A) and component (B) are supported on a carrier (C).

In the olefin polymerization method of the present invention, the polymerization or copolymerization of olefin is carried out in the presence of the above-mentioned olefin polymerization catalyst to form an olefin polymer.

In the present invention, polymerization can be carried out using any one of liquid phase polymerization (such as solution polymerization or suspension polymerization) and gas phase polymerization methods.

Examples of inert hydrocarbon media for liquid phase polymerization include: aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as Cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene, and xylene; halogenated hydrocarbons, such as vinyl chloride, chlorobenzene, and methylene chloride; and mixtures of these hydrocarbons. Alkenes themselves can also be used as solvents.

When olefin polymerization is carried out using an olefin polymerization catalyst, ^the component (A) is used in an amount of ^{usually 10-12-10-2} moles, preferably ^10-10-10-3 moles, based on 1 liter of reaction volume. In the present invention, olefin polymerization can be performed with high polymerization activity even if component (A) is used in a relatively low concentration.

Component (B-1) is used in such an amount that the molar ratio ((B-1)/(M)) of component (B-1) to transition metal atoms (M) in component (A) is usually 0.01-100,000 , preferably 0.05-50,000.

Component (B-2) is used in an amount such that the molar ratio ((B-2)/(M)) of aluminum atoms in component (B-2) to transition metal atoms (M) in component (A) is usually 10-500,000, preferably 20-100,000.

Component (B-3) is used in an amount such that the molar ratio ((B-3)/(M)) of component (B-3) to the transition metal atom (M) in component (A) is generally 1-10 , preferably 1-5.

The amount of component (D) for component (B) is as follows: for component (B-1), (D)/(B-1) molar ratio is usually 0.01-10, preferably 0.1-5; Part (B-2), the molar ratio ((D)/(B-2)) of aluminum atoms in component (D) and component (B-2) is usually 0.001-2, preferably 0.005-1; For component (B-3), the (D)/(B-3) molar ratio is usually 0.01-10, preferably 0.1-5.

In olefin polymerization using an olefin polymerization catalyst, the polymerization temperature may generally be in the range of -50°C to 200°C, preferably 0-170°C. The polymerization pressure can usually range from atmospheric pressure to 100 kg/ ^cm2 , preferably from atmospheric pressure to 50 kg/ ^cm2 . The polymerization can be carried out using any of batch, semi-continuous and continuous methods. It is also possible to carry out the polymerization in two or more steps under different reaction conditions.

The molecular weight of the resulting polymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. In addition, the molecular weight can also be adjusted by changing the type of component (B).

Examples of olefins that can be polymerized using olefin polymerization catalysts include:

Alpha-olefins with 2-20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene ene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene;

Cycloolefins containing 3-20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1,4 , 5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene;

Polar monomers such as unsaturated carboxylic acids, including α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo[2,2 ,1]-5-heptene-2,3-dicarboxylic acid; metal salts of these acids, such as sodium, potassium, lithium, zinc, magnesium and calcium salts; esters of unsaturated carboxylic acids, including α , β-unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate , methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl esters such as vinyl acetate, Vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; and unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate esters and monoglycidyl itaconate.

Vinylcyclohexane, dienes and polyenes may also be used.

Dienes and polyenes are cyclic or chain compounds having 4-30 carbon atoms, preferably 4-20 carbon atoms, and containing two or more double bonds. Examples of such compounds include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexanediene ene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene;

7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;

Aromatic vinyl compounds, including mono- or polyalkylene styrenes, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene;

Styrene derivatives with functional groups, such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chloro Styrene and divinylbenzene; and also

3-phenylpropene, 4-phenylpropene and alpha-methylstyrene.

The olefin polymerization catalyst of the present invention exhibits high polymerization activity, and a polymer having a narrow molecular weight distribution can be obtained by using this catalyst. When two or more olefins are copolymerized, an olefin copolymer with a narrow composition distribution can be obtained.

The olefin polymerization catalysts of the present invention can also be used to copolymerize alpha-olefins and polar monomers. Examples of the ?-olefin used here include the same straight or branched ?-olefins having 2 to 30 carbon atoms (preferably 2 to 20 carbon atoms) as mentioned above. Examples of the polar monomer used here include the same monomers as described above.

The olefin polymerization catalyst of the present invention can also be used for copolymerizing α-olefins and conjugated dienes.

Examples of the ?-olefin used here include the same straight or branched ?-olefins having 2 to 30 carbon atoms (preferably 2 to 20 carbon atoms) as mentioned above. Among them, preferred are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularly preferred are ethylene and propylene. These α-olefins may be used alone or in combination of two or more.

Examples of conjugated dienes include aliphatic conjugated dienes containing 4-30 carbon atoms, preferably 4-20 carbon atoms, such as 1,3-butadiene, isoprene, chloroprene , 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene and 1,3-octadiene. These conjugated dienes may be used alone or in combination of two or more.

According to the present invention, non-conjugated dienes or polyenes can also be used to copolymerize alpha-olefins and conjugated dienes. Examples of non-conjugated dienes and polyenes include: 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene ene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene , 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene.

The invention is also illustrated with reference to the following examples, but it should be construed that the invention is by no means limited to these examples.

The structure of the compound obtained in the synthesis examples is determined in the following manner: 270MHz 1H-NMR (Japan Electron Optics Laboratory GSH-270 model), FT-IR (SHIMADZUFTIR-8200D model), FD-mass spectrometry (Japan Electron Optics Laboratory SX -102A model), metal content analysis (analysis by ICP method after dry ashing and dissolved in dilute nitric acid, equipment: SHIMADZU ICPS-8000 model) and elemental analysis of carbon, hydrogen and nitrogen (Helaus CHNO model). Intrinsic viscosity (η) is measured in decahydronaphthalene at 135°C.

Synthesis Example 1

Synthesis of compound shown in chemical formula (L1)

In a 100 ml reactor, 1.0 g (10.7 mmol) of aniline, 3.3 g (32.2 mmol) of concentrated hydrochloric acid and 5.4 ml of water were vigorously stirred to obtain a solution which was cooled to 0° C. with ice. To this solution, a solution obtained by dissolving 0.75 g (10.7 mmol) of sodium nitrite (purity: 98.5%) in 2.6 ml of water was slowly added with stirring to keep the temperature not higher than 5°C. After the dropwise addition was completed, the resulting mixture was stirred at 0° C. for 1 hour to obtain an aqueous solution of benzenediazonium chloride. In another 100 ml reactor, 2.22 g (10.7 mmol) of 2,4-di-tert-butylphenol were dissolved in 3 ml of tetrahydrofuran. To this solution was added an aqueous solution obtained by dissolving 2.22 g (53 mmol) of sodium hydroxide in 22 ml of water, and the resulting mixture was cooled to 0°C with ice. Then, the aqueous solution of benzenediazonium chloride prepared above was slowly added dropwise with stirring, and the mixture was further stirred at 0°C for 1.5 hours. After the temperature of the reaction solution was raised to room temperature, 30 ml of diethyl ether was added to the reaction solution to separate the solution into two phases. Then, the oily phase was washed with dilute hydrochloric acid and dried over sodium sulfate. The solvent was distilled off from the solution, and the residue was purified with a silica gel column to obtain 2.56 g (yield: 77%) of a dark red solid of a compound represented by the following formula (L1).

FD-mass spectrum: (M ⁺ )310

¹ H-NMR (CDCl ₃ ): 1.38(s, 9H), 1.47(s, 9H), 7.40-7.95(m, 7H), 13.71(s, 1H)

Synthesis of compound shown in chemical formula (a-1)

1.07 g (3.45 mmol) of the compound represented by the chemical formula (L1) and 21 ml of diethyl ether were added to a 100 ml reactor thoroughly dried and purged with argon, cooled to -78°C and stirred. To the resulting mixture, 2.25 ml of n-butyllithium (1.60 mmol/ml n-hexane solution, 3.45 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature and stirred at room temperature for 3 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of 3.40 ml of titanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.70 mmol) and 21 ml of diethyl ether which had been previously cooled to -78°C.

After the dropwise addition was completed, the reaction solution was slowly warmed to room temperature and stirred. Stirring of the reaction solution was continued at room temperature for 4 hours, and then the solution was filtered through a glass filter to remove insoluble matter. The filtrate was concentrated under reduced pressure to precipitate a solid. The solid was dissolved in 2 ml of pentane and allowed to stand at -20°C to precipitate crystals. The crystals were vacuum-dried to obtain 0.80 g (1.01 mmol, yield: 59%) of red-black crystals of a compound represented by the following formula (a-1).

FD-mass spectrum: (M ⁺ )736

¹ H-NMR (CDCl ₃ ): 1.31 (s, 18H), 1.49 (s, 18H), 7.00-7.95 (m, 14H)

Elemental analysis: Ti: 6.7% (calculated value: 6.5%)

Synthesis Example 2

Synthesis of compound shown in chemical formula (b-1)

1.07 g (3.45 mmol) of the compound represented by the chemical formula (L1) and 21 ml of diethyl ether were added to a 100 ml reactor thoroughly dried and purged with argon, cooled to -78°C and stirred. To the resulting mixture, 2.25 ml of n-butyllithium (1.61 mmol/ml n-hexane solution, 3.45 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature and stirred at room temperature for 3 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of 0.40 g (1.71 mmol) of zirconium tetrachloride and 21 ml of diethyl ether previously cooled to -78°C.

After the dropwise addition was completed, the reaction solution was slowly warmed to room temperature and stirred. Stirring of the reaction solution was continued at room temperature for 8 hours, and then the solution was filtered through a glass filter to remove insoluble matter. The filtrate was concentrated under reduced pressure to precipitate a solid. The solid was dissolved in 2 ml of pentane and allowed to stand at -20°C to precipitate crystals. The crystals were vacuum-dried to obtain 1.30 g (1.66 mmol, yield: 97%) of red-black crystals of a compound represented by the following formula (b-1).

FD-mass spectrum: (M ⁺ )780

¹ H-NMR (CDCl ₃ ): 1.37(s, 18H), 1.47(s, 18H), 6.75-7.95(m, 14H)

Elemental analysis: Zr: 11.4% (calculated value: 11.7%)

Synthesis Example 3

Synthesis of compound shown in chemical formula (L2)

Using 2.0g (21.6mmol) aniline and 3.6g (21.5mmol) 2-tert-butyl-4-methylphenol as raw materials, synthesized in the same way as the compound shown in the synthetic chemical formula (L1) in Synthesis Example 1 to obtain 4.98 grams (18.6 mmol, yield: 86%) Vermilion solid of the compound represented by the following chemical formula (L2).

FD-mass spectrum: (M ⁺ )268

¹ H-NMR (CDCl ₃ ): 1.46(s, 9H), 2.37(s, 3H), 7.15-7.95(m, 7H), 13.62(s, 1H)

Synthesis of compound shown in chemical formula (a-2)

Use the compound shown in 1.02 g (3.82mmol) chemical formula (L2), synthetically obtain 0.34 gram (0.52mmol, productive rate: 27%) by the following Dark brown powder of the compound represented by chemical formula (a-2).

FD-mass spectrum: (M ⁺ )653

¹ H-NMR (CDCl ₃ ): 1.46 (s, 18H), 2.30-2.40 (m, 6H), 7.00-7.90 (m, 14H)

Elemental analysis: Ti: 7.3% (calculated value: 7.3%)

Synthesis Example 4

Synthesis of compound shown in chemical formula (b-2)

Use the compound shown in 1.02g (3.8mmol) chemical formula (L2), synthesize and obtain 0.22 gram (0.32mmol, productive rate: 17%) by the following Reddish-brown crystals of the compound represented by chemical formula (b-2).

FD-mass spectrum: (M ⁺ )696

¹ H-NMR (CDCl ₃ ): 1.47 (s, 18H), 2.38 (s, 6H), 6.95-7.90 (m, 14H)

Elemental analysis: Zr: 13.2% (calculated value: 13.1%)

Synthesis Example 5

Synthesis of compound shown in chemical formula (L3)

Using 1.77g (10.0mmol) 2,6-diisopropylaniline and 1.94g (10.0mmol) 2,4-dimethylphenyltrimethylsilyl ether as raw materials, synthetic chemical formula in Synthesis Example 1 The compound represented by (L1) was synthesized in the same manner to obtain 1.83 g (5.3 mmol, yield: 53%) of a deep red solid represented by the following chemical formula (L3).

FD-mass spectrum: (M ⁺ )346

¹ H-NMR (CDCl ₃ ): 0.03(s, 9H), 1.15(d, 12H), 2.36(s, 3H), 2.50(s, 3H), 2.79(dq, 2H), 7.05-7.95(m, 5H)

Synthesis of compound shown in chemical formula (c-3)

Add 0.47g (3.6mmol) cobalt dichloride and 15ml THF in the 100 milliliter reactors that have purged thoroughly with argon, add the solution of the compound shown in 1.21g (3.5mmol) chemical formula (L3) in 10ml THF to A yellow material precipitated. The mixture was stirred for 1 hour, filtered through a glass filter and the precipitate was separated. The resulting solid was reprecipitated with a diethyl ether/dichloromethane solution, washed with 50 ml of hexane and dried in vacuo to obtain 1.13 g (yield: 68%) of a compound represented by the following chemical formula (c-3) as a brown powder.

FD-mass spectrum: (M ⁺ )476

Elemental analysis: Co: 12.5% (calculated value: 12.4%)

Example 1

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (a-1) obtained in Synthesis Example 1 was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.10 g of polyethylene.

The polymerization activity was 42 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 19.7 dl/g.

Example 2

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (a-1) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were sequentially added to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Hydrochloric acid was then added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.39 g of polyethylene.

The polymerization activity was 155 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 25.9 dl/g.

Example 3

Polymerization was carried out under the same conditions as in Example 1 using the compound represented by the chemical formula (b-1). As a result, 0.07 g of polyethylene was obtained. The polymerization activity was 29 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 9.5 dl/g.

Example 4

Polymerization was carried out under the same conditions as in Example 2 using the compound represented by the chemical formula (b-1). As a result, 0.32 g of polyethylene was obtained. The polymerization activity was 128 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 11.2 dl/g.

Example 5

Polymerization was carried out under the same conditions as in Example 1 using the compound represented by the chemical formula (a-2). As a result, 0.10 g of polyethylene was obtained. The polymerization activity was 40 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 16.9 dl/g.

Example 6

Polymerization was carried out under the same conditions as in Example 2 using the compound represented by the chemical formula (a-2). As a result, 0.70 g of polyethylene was obtained. The polymerization activity was 280 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 26.3 dl/g.

Example 7

Polymerization was carried out under the same conditions as in Example 1 using the compound represented by chemical formula (b-2). As a result, 0.06 g of polyethylene was obtained. The polymerization activity was 24 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 9.7 dl/g.

Example 8

Polymerization was carried out under the same conditions as in Example 2 using the compound represented by chemical formula (b-2). As a result, 0.50 g of polyethylene was obtained. The polymerization activity was 200 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 5.6 dl/g.

Example 9

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum was added, and then 0.005 mmol of the compound represented by the chemical formula (c-3) was added to initiate polymerization. The reaction was carried out at 250° C. for 1 hour in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Hydrochloric acid was then added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.03 g of polyethylene. The polymerization activity was 12 kg/mol-Co·hr, and the intrinsic viscosity (η) of polyethylene was 3.9 dl/g.

Synthesis Example 6

Synthesis of compound shown in chemical formula (L4)

10 ml of ethanol, 0.61 g (6.52 mmol) of aniline and 0.95 g (5.43 mmol) of 1-(2,4,6-triisopropylphenyl)-1 were added to a 100 ml reactor thoroughly purged with nitrogen, 3-Butanedione, add 5 g molecular sieve 3A and 1 ml acetic acid. Then, the mixture was heated to 80° C. and stirred for 3 hours. The reaction solution was concentrated under reduced pressure, and the concentrate was purified with a silica gel column to obtain 0.60 g (1.53 mmol, yield: 47%) of off-white crystals of the compound represented by the following chemical formula (L4).

FD-mass spectrum: (M ⁺ )391

¹ H-NMR (CDCl ₃ ): 1.2-1.4 (m, 18H), 1.59 (s, 1H), 2.09 (s, 3H), 2.90 (dt, 1H), 3.11 (dt, 2H), 5.38 (s, 1H), 7.00(s, 2H), 7.1-7.5(m, 5H)

Synthesis of compound shown in chemical formula (a-4)

Into a thoroughly dried and argon-purged 100 ml reactor were added 0.31 g (0.85 mmol) of the compound represented by the chemical formula (L4) and 10 ml of diethyl ether, cooled to -78°C and stirred. To the resulting mixture, 0.53 ml of n-butyllithium (1.61 mmol/ml n-hexane solution, 0.85 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature and stirred at room temperature for 3 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of 0.84 ml of titanium tetrachloride solution (0.5 mmol/ml in heptane, 0.42 mmol) and 6 ml of tetrahydrofuran which had been previously cooled to -78°C. After the dropwise addition was completed, the reaction solution was slowly warmed to room temperature and stirred. Stirring of the reaction solution was continued at room temperature for 8 hours, and the solvent was distilled off from the solution under reduced pressure. The residue was dissolved in 10 ml of dichloromethane, and the solution was filtered through a glass filter to remove insoluble matter. The filtrate was concentrated under reduced pressure to precipitate a solid. The solid was recrystallized from hexane and dried in vacuo to obtain 0.17 g (0.20 mmol, yield: 48%) of a dark brown powder of the compound represented by the following formula (a-4).

FD-mass spectrum: (M ⁺ )842

Elemental analysis: Ti: 6.0%

Synthesis Example 7

Synthesis of compound shown in chemical formula (b-4)

Into a thoroughly dried and argon-purged 100 ml reactor were added 0.49 g (1.35 mmol) of the compound represented by the chemical formula (L4), 12 ml of diethyl ether and 18 ml of tetrahydrofuran, cooled to -78°C and stirred. To the resulting mixture, 0.84 ml of n-butyllithium (1.61 mmol/ml n-hexane solution, 1.35 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature and stirred at room temperature for 3 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of 0.25 g (0.67 mmol) of zirconium tetrachloride-THF complex and 10 ml of tetrahydrofuran previously cooled to -78°C. After the dropwise addition was completed, the reaction solution was slowly warmed to room temperature and stirred. Stirring of the reaction solution was continued at room temperature for 8 hours, and the solvent was distilled off from the solution under reduced pressure. The residue was dissolved in 10 ml of dichloromethane, and the solution was filtered through a glass filter to remove insoluble matter. The filtrate was concentrated under reduced pressure to precipitate a solid. The solid was recrystallized from hexane and dried in vacuo to obtain 0.36 g (0.41 mmol, yield: 61%) of a yellow powder of the compound represented by the following formula (b-4).

FD-mass spectrum: (M ⁺ )887

Elemental analysis: Zr: 10.5%

Synthesis Example 8

Synthesis of compound shown in chemical formula (L5)

To a 100 mL reactor purged thoroughly with nitrogen, 10 mL of ethanol, 0.61 g (6.52 mmol) of aniline and 1.11 g (5.43 mmol) of 1-(2,4,6-trimethylphenyl)-1,3 - Diacetyl, add 5 g molecular sieve 3A and 1 ml acetic acid. Then, the mixture was heated to 80° C. and stirred for 3 hours. The reaction solution was concentrated under reduced pressure, and the concentrate was purified with a silica gel column to obtain 1.29 g (4.62 mmol, yield: 85%) of the compound represented by the following chemical formula (L5) as an orange oil.

FD-mass spectrum: (M ⁺ )279

Synthesis of compound shown in chemical formula (b-5)

Into a thoroughly dried and argon-purged 100 ml reactor were added 0.67 g (2.40 mmol) of the compound represented by the chemical formula (L5), 10 ml of diethyl ether and 5 ml of tetrahydrofuran, cooled to -78°C and stirred. To the resulting mixture, 1.61 ml of n-butyllithium (1.55 mmol/ml n-hexane solution, 2.50 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature and stirred at room temperature for 3 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of 0.25 g (0.67 mmol) of zirconium tetrachloride and 10 ml of tetrahydrofuran previously cooled to -78°C. After the dropwise addition was completed, the reaction solution was slowly warmed to room temperature and stirred. Stirring of the reaction solution was continued at room temperature for 8 hours, and the solvent was distilled off from the solution under reduced pressure. The residue was dissolved in 10 ml of dichloromethane, and the solution was filtered through a glass filter to remove insoluble matter. The filtrate was concentrated under reduced pressure to precipitate a solid. The solid was recrystallized from hexane and dried in vacuo to obtain 0.47 g (0.65 mmol, yield: 54%) of a yellow powder of a compound represented by the following formula (b-5).

FD-mass spectrum: (M ⁺ )718

¹ H-NMR (CDCl ₃ ): 2.00-2.50 (m, 24H), 5.20-5.60 (m, 2H), 6.75-6.95 (m, 4H), 7.10-7.50 (m, 10H)

Elemental analysis: Zr: 12.5%

Example 10

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (a-4) obtained in Synthesis Example 6 was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.10 g of polyethylene.

The polymerization activity was 40 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 6.5 dl/g.

Example 11

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (a-4) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere at atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Hydrochloric acid was then added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.30 g of polyethylene.

The polymerization activity was 120 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 4.1 dl/g.

Example 12

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (b-4) obtained in Synthesis Example 7 was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.60 g of polyethylene.

The polymerization activity was 60 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 6.8 dl/g.

Example 13

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (b-4) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere under normal pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Hydrochloric acid was then added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.30 g of polyethylene.

The polymerization activity was 120 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 6.8 dl/g.

Example 14

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (b-5) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Hydrochloric acid was then added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.20 g of polyethylene.

The polymerization activity was 80 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 7.5 dl/g.

Synthesis Example 9

Synthesis of compound shown in chemical formula (L6)

2.3 g (8.94 mmol) of 2,2'-iminodibenzoic acid and 50 ml of THF were added to a 500 ml reactor which had been thoroughly dried and purged with argon, and cooled to -20°C. While stirring at this temperature, 90 ml of a THF solution (0.3 M) of bis(1-methylpiperazin-4-yl)aluminum hydride was added dropwise. Then, the temperature of the system was raised, and the reaction was performed under reflux for 24 hours. The reaction solution was allowed to stand to cool to room temperature. To the solution was added 100 ml of diethyl ether, and then 150 ml of water was slowly added while cooling with ice. The oil layer obtained by phase separation was concentrated and separated by silica gel column chromatography to obtain 673 mg of 2,2'-iminodibenzaldehyde. Add 650mg (2.89mmol) 2,2'-iminobenzaldehyde, 699mg (5.77mmol) 2,6-dimethylaniline, 50ml dehydrated methanol and 0.2ml of acetic acid was added, and the reaction was carried out at room temperature for 12 hours. The solvent was distilled off from the reaction solution, and the residue was separated by silica gel column chromatography to obtain 237 mg (yield: 6.1%) of the compound represented by the following chemical formula (L6).

¹ H-NMR (CDCl ₃ , δ): 2.21(s, 12H), 4.96(s, 1H), 6.37-7.74(m, 14H), 8.21(2H)

Synthesis of compound shown in chemical formula (d-6)

Add 200 mg (0.46 mmol) of the compound represented by chemical formula (L6) and 20 ml THF to a 30 ml reactor that has been thoroughly dried and purged with argon, cooled to -78° C. and stirred. To the resulting mixture was added dropwise 2.9 ml of n-butyllithium-hexane-THF solution (0.16 M), slowly heated to room temperature and stirred for 1 hour to prepare a lithium salt solution. Add 58.7 mg (0.46 mmol) of ferrous chloride and 20 ml of THF to a 30 ml reactor that has been thoroughly dried and purged with argon, stirred at room temperature for 2 hours and cooled to -78°C. Then, the previously prepared lithium salt solution was added dropwise. After the dropwise addition was completed, the reaction solution was slowly heated to room temperature, and the solution was stirred at room temperature for 3 hours. Then, the solution was filtered through a glass filter. The filtrate was concentrated to obtain 5 ml of a concentrate, to which was added 5 ml of n-pentane. The resulting precipitate was filtered, washed with 10 ml of n-pentane, and dried under reduced pressure to obtain 203 mg (yield: 85%) of the compound represented by chemical formula (d-6).

FD-mass spectrum: (M ⁺ ): 521

Example 15

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (d-6) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under normal pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.01 g of polyethylene. The polymerization activity was 4 kg/mol-Fe·hr.

Synthesis Example 10

Synthesis of compound shown in chemical formula (a-6)

Add 100mg (0.23mmol) of the compound represented by the chemical formula (L6) and 20ml THF to a 30ml reactor that has been thoroughly dried and purged with argon, cooled to -78°C and stirred. To the resulting mixture was added dropwise 1.5 ml of n-butyllithium-hexane-THF solution (0.16 M), slowly heated to room temperature and stirred for 1 hour to prepare a lithium salt solution. Add 43.6 mg (0.23 mmol) of titanium tetrachloride and 20 ml of THF to a 30 ml reactor that has been thoroughly dried and purged with argon, stirred at room temperature for 2 hours and cooled to -78°C. Then, the previously prepared lithium salt solution was added dropwise. After the dropwise addition was completed, the reaction solution was slowly heated to room temperature, and the solution was stirred at room temperature for 3 hours. Then, the solution was filtered through a glass filter. The filtrate was concentrated to obtain 5 ml of a concentrate, to which was added 5 ml of n-pentane. The resulting precipitate was filtered, washed with 10 ml of n-pentane, and dried under reduced pressure to obtain 83 mg (yield: 62%) of the compound represented by the chemical formula (a-6).

FD-mass spectrum: (M ⁺ )584

Example 16

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (a-6) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under normal pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.05 g of polyethylene. The polymerization activity was 21 kg/mol-Ti·hr.

Synthetic Example 11

Synthesis of compound shown in chemical formula (b-6)

Add 200 mg (0.23 mmol) of the compound represented by the chemical formula (L6) and 20 ml of THF to a 30 ml reactor that has been thoroughly dried and purged with argon, cooled to -78° C. and stirred. To the resulting mixture was added dropwise 1.5 ml of n-butyllithium-hexane-THF solution (0.16 M), slowly heated to room temperature and stirred for 1 hour to prepare a lithium salt solution. Add 53.6 mg (0.23 mmol) of zirconium tetrachloride and 20 ml of THF to a 30 ml reactor that has been thoroughly dried and purged with argon, stirred at room temperature for 2 hours and cooled to -78°C. Then, the previously prepared lithium salt solution was added dropwise. After the dropwise addition was completed, the reaction solution was slowly heated to room temperature, and the solution was stirred at room temperature for 3 hours. Then, the solution was filtered through a glass filter. The filtrate was concentrated to obtain 5 ml of a concentrate, to which was added 5 ml of n-pentane. The resulting precipitate was filtered, washed with 10 ml of n-pentane, and dried under reduced pressure to obtain 53 mg (yield: 37%) of the compound represented by chemical formula (b-6).

FD-mass spectrum: (M ⁺ )626

Example 17

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (d-6) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction product was added to a large amount of methanol to precipitate the entire polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.12 g of polyethylene. The polymerization activity was 42 kg/mol-Zr·hr.

Synthetic Example 12

Synthesis of compound shown in chemical formula (L7)

Under argon at room temperature, 2.0 A solution of g (16.8 mmol) phthallactam in 10 ml THF. After stirring for 12 hours, 5 ml of 6N hydrochloric acid was added, followed by 50 ml of 10% _Na2CO3 aqueous _solution to terminate the reaction. The organic phase was separated, the solvent was distilled off, and column purification was performed to obtain 2.20 g (11.2 mmol, yield: 67%) of the corresponding formyl compound as yellow crystals.

0.79 g (4.0 mmol) of the formyl compound obtained above was dissolved in 1.0 g (10.0 mmol) of cyclohexylamine, and the solution was stirred at room temperature for 12 hours. The mixture liquid was vacuum-dried to remove excess cyclohexylamine, thereby obtaining 1.13 g (4.0 mmol, yield: 100%) of a yellow oil of the compound represented by Chemical Formula (L7).

¹ H-NMR (CDCl ₃ ): 1.2-2.0 (m, 10H), 3.19 (dt, 1H), 6.7-7.4 (m, 9H), 8.43 (s, 1H), 11.47 (brs, 1H)

Synthesis of compound shown in chemical formula (a-7)

Into a thoroughly dried and argon-purged 100 ml reactor were added 0.56 g (2.0 mmol) of the compound represented by the chemical formula (L7) and 10 ml of diethyl ether, cooled to -78°C and stirred. To the resulting mixture, 1.24 ml of n-butyllithium (1.61 N n-hexane solution, 2.0 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature to prepare a lithium salt solution. This solution was added dropwise to a mixture of 2.0 ml of a 0.5N titanium tetrachloride-decane solution and diethyl ether previously cooled to -78°C. The solution was slowly warmed to room temperature and stirred for 12 hours. Then, the reaction solution was filtered and washed with dichloromethane. The solvent was distilled off from the filtrate. The resulting solid was reprecipitated with diethyl ether/hexane to obtain 0.21 g (yield: 31%) of a reddish-brown powder of the compound represented by the following chemical formula (a-7).

¹ H-NMR (CDCl ₃ ): 0.9-2.4 (m, 20H), 3.3-3.6 (m, 2H), 6.8-7.8 (m, 18H), 8.60 (brs, 2H)

Synthetic Example 13

Synthesis of compound shown in chemical formula (b-7)

Into a 100 ml reactor thoroughly dried and purged with argon, 0.56 g (2.0 mmol) of the compound represented by the chemical formula (L7) and 5 ml of diethyl ether were added, cooled to -78°C and stirred. To the resulting mixture, 1.24 ml of n-butyllithium (1.61 N n-hexane solution, 2.0 mmol) was added dropwise for 5 minutes, and the solution was slowly heated to room temperature to prepare a lithium salt solution. This solution was added dropwise to a THF solution of 0.38 g (1.0 mmol) of zirconium tetrachloride/2THF complex previously cooled to -78°C. The resulting solution was slowly warmed to room temperature and stirred for 12 hours. Then, the solvent was distilled off, and the resulting solid was washed with dichloromethane and filtered. The solvent was distilled off from the filtrate, and the obtained solid was reslurried in hexane to obtain 0.37 g (yield: 52%) of the compound represented by the following chemical formula (b-7) as an orange powder.

¹ H-NMR (CDCl ₃ ): 1.0-2.0 (m, 20H), 3.78-3.98 (m, 2H), 6.8-7.5 (m, 18H), 8.1-8.3 (m, 2H)

FD-MS (M ⁺ ): 716

Example 18

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 1.25 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (a-7) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere at atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80° C. for 10 hours to obtain 0.09 g of polyethylene (PE).

The polymerization activity was 40 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 11.0 dl/g.

Example 19

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (a-7) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. The reaction was carried out at 25° C. for 15 minutes in an ethylene atmosphere at atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80° C. for 10 hours to obtain 0.15 g of polyethylene (PE).

The polymerization activity was 120 kg/mol-Ti·hr, and the intrinsic viscosity (η) of polyethylene was 30.2 dl/g.

Example 20

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 1.25 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (b-7) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80° C. for 10 hours to obtain 0.08 g of polyethylene (PE).

The polymerization activity was 30 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 16.9 dl/g.

Example 21

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (b-7) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization.

The reaction was carried out at 25° C. for 20 minutes in an ethylene atmosphere at atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80° C. for 10 hours to obtain 0.33 g of polyethylene (PE).

The polymerization activity was 200 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 9.44 dl/g.

Synthetic Example 14

Synthesis of compound shown in chemical formula (L8)

Add 1.32g (60% in oil, 33.0mmol) sodium hydride and 10ml DMF in the 50ml reactor that has been purged with nitrogen, slowly add dropwise 5.63g (30.0mmol) 3-tert-butyl salicylaldehyde in 5ml DMF solution while cooling with ice. The mixture was stirred at room temperature for 30 minutes, then a DMF solution of 4.82 g (39.0 mmol) of dimethylthiocarbamoyl chloride was added dropwise. The resulting mixture was stirred overnight at room temperature, then treated with water and purified by column to give 5.39 g of a yellow solid.

4.50 g of the yellow solid was heat-treated at 130°C in a nitrogen atmosphere, whereby an exchange reaction in which oxygen atoms were exchanged for sulfur atoms proceeded. The resulting solid was column purified and dissolved in 30 ml of ethanol. In the presence of 0.1ml acetic acid, this solution was reacted with 0.90g (9.68mmol) aniline at room temperature for 5.5 hours, and then column purification was carried out to obtain 0.21g (0.62mmol, yield: 13%) shown in the following chemical formula (L8) Compound as white crystals.

¹ H-NMR (CDCl ₃ ): 1.40(s, 9H), 3.01(s, 3H), 3.22(s, 3H), 6.6-8.0(m, 8H), 8.38(s, 1H)

Synthesis of compound shown in chemical formula (b-8)

In a thoroughly dried and argon-purged 100 ml reactor, 0.04 g (0.11 mmol) of zirconium tetrachloride/2THF complex was dissolved in 5 ml THF, and the solution was cooled to -78°C. In this solution, the solution of the compound shown in 0.11g (0.22mmol) chemical formula (L8) in 5ml THF was added dropwise, heated to room temperature and stirred for 4 days. After distilling off the solvent, the resulting solid was washed with dichloromethane and filtered. The solvent was distilled off from the filtrate, and the resulting solid was reslurried in hexane to obtain a yellow powder of the compound represented by the following chemical formula (b-8).

FD-MS (M ⁺ ): 698

Example 22

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 1.25 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (b-8) was added to initiate polymerization. The reaction was carried out at 25° C. for 30 minutes in an ethylene atmosphere under atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80°C for 10 hours to obtain 0.35 g of polyethylene.

The polymerization activity was 140 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 4.2 dl/g.

Example 23

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, and then 0.005 mmol of the compound represented by the chemical formula (b-8) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere at atmospheric pressure. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter. The resulting polymer was vacuum-dried at 80° C. for 10 hours to obtain 0.30 g of polyethylene (PE).

The polymerization activity was 60 kg/mol-Zr·hr, and the intrinsic viscosity (η) of polyethylene was 9.2 dl/g.

Synthetic Example 15

Synthesis of compound shown in chemical formula (L9)

To a 100 mL reactor purged thoroughly with nitrogen, add 10 mL of ethanol, 0.61 g (5.00 mmol) of 2,6-dimethylaniline and 0.95 g (3.3 mmol) of 1-(2,4,6-triisopropyl phenyl)-1,3-butanedione, add 5 g molecular sieve 3A and 1 ml acetic acid. Then, the mixture was heated to 80° C. and stirred for 3 hours. The reaction solution was concentrated under reduced pressure, and the concentrate was purified with a silica gel column to obtain off-white crystals of a compound. This compound was dissolved in diethyl ether and reacted with diazomethane to obtain 0.60 g (1.48 mmol, yield: 43%) of a compound represented by the following chemical formula (L9).

¹ H-NMR (CDCl ₃ ): 1.2-1.4 (m, 18H), 1.62 (s, 1H), 2.11 (s, 3H), 2.30 (s, 3H), 2.35 (s, 3H), 2.92 (dt, 1H), 3.14(dt, 2H), 3.76(s, 3H), 5.40(s, 1H), 7.00(s, 2H), 7.3-7.5(m, 3H)

Synthesis of compound shown in chemical formula (c-9)

Add 0.19g (1.50mmol) cobalt dichloride and 15ml THF in 100 milliliters of reactors that have purged thoroughly with argon, add 0.60g (1.48mmol) compound represented by chemical formula (L9) therein in 10ml THF at room temperature The solution in was then stirred for 1 hour. The precipitate was separated by filtration, and the resulting solid was washed with dichloromethane/diethyl ether to obtain 0.18 g (yield: 23%) of a compound represented by the following chemical formula (c-9) as a brown powder.

FD-MS: (M ⁺ )535

Example 24

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 1.1875 mmol (in terms of aluminum atoms) of methylaluminoxane was added, and then 0.005 mmol of the compound represented by the chemical formula (c-9) was added to initiate polymerization. The reaction was carried out at 25° C. for 60 minutes in an ethylene atmosphere at atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter to obtain polyethylene.

Synthesis Example 10

Synthesis of compounds shown in chemical formula (L10)

Add 100ml ethanol, 5.32g (30.0mmol) 2,6-dimethylaniline and 3.75g (20.0mmol) 3-tert-butylsalicylaldehyde in the 200ml reactor that has been purged thoroughly with nitrogen, add 0.5 ml acetic acid. Then, the mixture was stirred at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure and purified with a silica gel column to obtain a compound as a yellow oil. This compound was dissolved in methanol and reacted with dimethylsulfuric acid to obtain 5.95 g (16.9 mmol, yield: 85%) of a compound represented by the following chemical formula (L10).

¹ H-NMR (CDCl ₃ ); 1.18(d, 12H), 1.49(s, 9H), 3.01(dt, 1H), 3.95(s, 3H), 6.9-7.5(m, 6H), 8.29(s, 1H)

Synthesis of compound shown in chemical formula (d-10)

Add 0.25g (2.0mmol) ferric dichloride and 15ml THF in the 100 milliliter reactor that has purged thoroughly with argon, add 0.70g (2.0mmol) compound represented by chemical formula (L10) therein in 10ml THF at room temperature The solution in was then stirred for 1 hour. The precipitate was separated by filtration, and the obtained solid was washed with dichloromethane/diethyl ether to obtain 0.09 g (yield: 9%) of a compound represented by the following chemical formula (d-10) as a brown powder.

FD-MS: (M ⁺ )478

Example 25

Into a 500 ml glass autoclave purged thoroughly with nitrogen was added 250 ml of toluene and the liquid and gas phases were saturated with 100 l/h of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum (TIBA) was added, followed by 0.005 mmol of the compound represented by the chemical formula (d-10) and 0.006 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate to initiate polymerization. The reaction was carried out at 25° C. for 1 hour in an ethylene atmosphere under atmospheric pressure. Then, a small amount of isobutanol was added to terminate the polymerization. After the polymerization reaction was completed, the reaction mixture was added to a large amount of methanol to precipitate all the polymer. Then, hydrochloric acid was added, and the mixture was filtered through a glass filter to obtain polyethylene.

Claims (13)

1. An olefin polymerization catalyst comprising a transition metal compound (A-1) represented by the following general formula (I): Wherein, M is a transition metal atom selected from Group 4 and Group 8-10 of the Periodic Table of Elements, m is an integer of 1-3, Q is a nitrogen atom or a carbon atom with a substituent R ² , A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom, ^R is a hydrogen atom or a phenyl group, which is unsubstituted or substituted by methyl, isopropyl or tert-butyl, R ² is a hydrogen atom or a C ₁ -C ₆ alkyl group, R ³ and R ⁴ are connected together to form a benzene ring which is unsubstituted or substituted by methyl, isopropyl or tert-butyl, or each of R ³ and R ⁴ is a hydrogen atom, unsubstituted or substituted by methyl or Isopropyl substituted phenyl, R ⁵ is a hydrogen atom, C ₁ -C ₆ alkyl, phenyl or silyl, the silyl is unsubstituted or substituted by C ₁ -C ₆ alkyl, n is a number satisfying the valence of M, X is a halogen atom. 2. olefin polymerization catalyst as claimed in claim 1 is characterized in that described transition metal compound (A-1) is the transition metal compound that Q in the formula (I) is the carbon atom that has substituent R ² , and it uses The following general formula (Ia) represents: Wherein, M, m, A, R ¹ -R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁶ , n and X in the general formula (I). 3. olefin polymerization catalyst as claimed in claim 2 is characterized in that described transition metal compound (A-1) is R among the formula (Ia) ³ and R ⁴ link together and form the transition metal compound of an aromatic ring, it Express with following formula (Ib):

Wherein, M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n and X are the same as M, m, A, R ¹ , R ² , R ⁵ , R ⁶ , n in general formula (I) has the same meaning as X, R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁶ in the general formula (I), R ¹ , R ² and R ⁵ -R ¹⁰ are the same or different, and two or more of them are connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ are the same or different, a group of R ¹ , R ² , R 5 -R 10 included in one ligand is the same as a group of R ⁵ -R ¹⁰ included in another ligand R ¹ , R ² , R ⁵ -R ¹⁰ are connected. 4. The olefin polymerization catalyst as claimed in claim 1, characterized in that the transition metal compound (A-1) is Q in the general formula (I) is a nitrogen atom and R ³ and R ⁴ are connected together into an aromatic ring A transition metal compound represented by the following formula (Ic):

Wherein, M, m, A, R ¹ , R ⁵ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ⁵ , R ⁶ , n and X in general formula (I) , R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁶ in the general formula (I), R ¹ and R ⁵ -R ¹⁰ are the same or different, and two or more of them are connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ are the same or different, a group of R ¹ , R ⁵ -R ¹⁰ contained in one ligand is connected with a group of R ¹ , R ⁵ -R ¹⁰ contained in another ligand . 5. An olefin polymerization catalyst comprising a transition metal compound (A-2) represented by the following general formula (II): Wherein, M is a transition metal atom selected from Groups 3-5 and Groups 8-10 of the Periodic Table of Elements, m is an integer of 1-3, Q is a nitrogen atom or a carbon atom with a substituent R ² , A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom with a substituent R ⁶ , R ¹ -R ⁴ and R ⁶ are each hydrogen atom, C ₁ -C ₆ alkyl, unsubstituted or substituted by C ₁ -C ₆ alkyl silyl or phenyl, halogen atom, When m is 2, and a set of R ¹ -R ⁴ and R ⁶ groups contained in one ligand is connected to a set of R ¹ -R ⁴ and R ⁶ groups contained in another ligand , linking these groups together to form a linking group whose backbone contains 3 or more atoms, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group or a silicon-containing group. 6. The olefin polymerization catalyst as claimed in claim 5, characterized in that ^R3 and ^R4 are connected together to form an aromatic ring. 7. as claimed in claim 5 or 6 described olefin polymerization catalysts, it is characterized in that described transition metal compound (A-2) is the transition metal compound that Q is the carbon atom that has substituent R in formula ( ^II ), it Represented by the following general formula (II-a):

Wherein, M, m, A, R ¹ -R ⁴ , R ⁶ , n and X have the same meanings as M, m, A, R ¹ -R ⁴ , R ⁶ , n and X in general formula (II) . 8. olefin polymerization catalyst as claimed in claim 7 is characterized in that transition metal compound (A-2) is formula (II-a) in R ³ and R ⁴ are connected into the transition metal compound of an aromatic ring together, it uses The following formula (II-b) represents:

Wherein, M, m, A, R ¹ , R ² , R ⁶ , n and X have the same meanings as M, m, A, R ¹ , R ² , R ⁶ , n and X in the general formula (II) , When m is 1, A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent ^R6 , and when m is 2 or greater, multiple A are the same or different, and they are respectively an oxygen atom, a sulfur atom, a selenium atom Or a nitrogen atom with a substituent R ⁶ , and at least one A is a sulfur atom, a selenium atom or a nitrogen atom with a substituent R ⁶ , R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴ and R ⁶ in the general formula (II), R ¹ , R ² and R ⁶ -R ¹⁰ are the same or different, and two or more of them are connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ² , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ are the same or different, a group of R ¹ , R ² , R ⁶ -R ¹⁰ included in one ligand is the same as a group of R ¹ , R included in another ligand ^2. R ⁶ -R ¹⁰ are connected. 9. The olefin polymerization catalyst as claimed in claim 5 or 6, characterized in that the transition metal compound (A-2) is a transition in which Q is a nitrogen atom and R ^{and R} are connected together into an aromatic ring in the formula (II). A metal compound represented by the following formula (II-c):

Wherein, M, m, A, R ¹ , R ⁶ , n and X have the same meaning as M, m, A, R ¹ , R ⁶ , n and X in general formula (II), R ⁷ -R ¹⁰ have the same meaning as R ¹ -R ⁴ and R ⁶ in the general formula (II), R ¹ and R ⁶ -R ¹⁰ are the same or different, and two or more of them are connected to each other to form a ring. When m is 2 or greater, multiple R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ Or R ¹⁰ is the same or different, a group of R ¹ , R ⁶ -R ¹⁰ contained in one ligand is connected with a group of R ¹ , R ⁶ -R ¹⁰ contained in another ligand. 10. The olefin polymerization catalyst according to any one of claims 1-9, further comprising at least one compound (B) selected from: (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, or (B-3) A compound that reacts with the transition metal compound (A-1) or (A-2) to form an ion pair. 11. The olefin polymerization catalyst according to claim 10, further comprising a carrier (C). 12. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst as claimed in claim 1. 13. A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst as claimed in claim 5.

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